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Cigarette Smoking Man[]

Main article: Cigarette Smoking Man

Krycek first started working for the Cigarette Smoking Man in or before 1994. In that year, the Cigarette Smoking Man sent Krycek to work on a case with Agent Mulder. After the investigation, Krycek returned to the Cigarette Smoking Man and reported his findings regarding Mulder and his former partner, Agent Scully, both of whom represented a problem to Krycek and the Cigarette Smoking Man — (Sleepless). After using his position to sabotage a potential rescue of Scully by Mulder, at the CSM's behest, Krycek eventually was forced to flee the Bureau and work directly for his superior.

Roughly a year later, Krycek was enlisted as part of a plot to destroy Fox Mulder, after the agent had some in to possession of classified defense department files concerning the project to create alien-human hybrids. At the behest of the Syndicate, Krycek poisoned Fox Mulder's water supply, exposing Mulder to a substance that caused erratic, aggressive behavior. Krycek then killed William Mulder in an attempt to frame agent Mulder for the murder — (Anasazi). Shortly after these events, Krycek and two other agents of the Syndicate assaulted Walter Skinner, stealing the digital copy of the aforementioned files. While has was in possession of the digital tape containing the files, the Smoking Man attempted to eliminate both the tape and Krycek by means of a car bomb. Krycek escaped, and took the tape with him, threatening to expose the Syndicate and the contents of the files if any further attempts were made on his life. This led to Krycek's hatred of the Smoking Man.

Their following encounters would be characterized by extreme tension, with Krycek often holding himself back from killing his former mentor and superior. His hatred was further deepened when Krycek, while under the control of the alien virus, was locked underground in a missile silo and left for dead by the Smoking Man. — (Apocrypha)

Their next encounter came in 1998, when Krycek, now a member of the Syndicate's agents once again, is sent to retrieve the Smoking Man, who had gone in to hiding after his colleagues attempted to kill him for his poor handling of Mulder. Upon finding him, Krycek seemed tempted to simply kill him, rather than bring him back. The Smoking Man clearly recognized this, inviting Krycek to shoot. Later, while serving as the driver for the Well Manicured Man, Krycek offers to run the Smoking Man down in a vacant lot where they had met. He is not allowed to do so, and instead satisfies himself with making a close pass while driving off. — (The End)

Subsequently, Krycek often had to restrain himself from killing the Cigarette Smoking Man, but finally made an attempt on his life in 2000, by throwing the Cigarette Smoking Man down a flight of stairs. — (Requiem)

Fox Mulder[]

Main article: Fox Mulder

Krycek first met Fox Mulder in 1994. Mulder was transcribing wiretap tape at FBI's Headquarters when Krycek alerted Mulder that he was present. Krycek had been assigned to a case Mulder had requested but agreed to work with him as an investigative partner and revealed everything he had learned about the case.

However, Mulder was at first extremely reluctant to work with him. At one point, Mulder acted as if he had accepted Krycek as his new partner but ditched him while he had been obtaining a car for their investigation.

Krycek acted as if he was interested in Mulder's unlikely beliefs and even that he believed the same things as Mulder. — (Sleepless).

Krycek later selected Mulder – despite the fact that the two were often at odds with one another – to intercept the Syndicate courier with the alien rock from Tunguska, although this ultimately led to Krycek leaving Mulder in a Siberian gulag — (Tunguska). Krycek also helped Mulder to learn the location of the alien rebel captured by the Syndicate, kissing Mulder on the cheek when he delivered the information — (The Red and the Black). When Krycek finally attempted to kill Mulder, he was extremely reluctant to do so, hesitating for so long that Skinner finally arrived to prevent him. In their final conversation, it is implied that the reason Krycek often spared and assisted Mulder over the years, was that he held out some hope that Mulder would eventually be able to stop the plans for alien colonization. — (Existence)

Dana Scully[]

Main article: Dana Scully

When Krycek was sent to work with Mulder in 1994, he learned from the Cigarette Smoking Man that Mulder's former partner, Dana Scully, was a problem.

After he started working with Mulder, Krycek met Scully at her place of work - the FBI Academy in Quantico, Virginia. She was wearing medical garb when they met, since she had been examining a victim's corpse for Mulder, and remarked that it was good to meet him. Krycek returned the comment by stating that it was also good to meet her and held out his hand, gesturing for a handshake, but Scully did not reciprocate. When she showed Mulder the corpse, Krycek acted as if he was troubled by the shocking sight of the deceased body by coughing loudly into his fist.

Krycek later reported to the Cigarette Smoking Man that Scully was a much larger problem than he had been told she was — (Sleepless). He also threatened Scully's life many times. In 1995 he and Luis Cardinal made an attempt on her life under the orders of the Cigarette Smoking Man but by accident they killed her sister Melissa. Following Fox Mulder's return on Earth, he appeared on Walter Skinner and blackmailed him in order to kill Scully's unborn baby — (Deadalive) and in return he would give him the vaccine to save Mulder's life.He also helped in her abduction (Ascension) by the Syndicate. In every interaction that they had, Scully seems mostly apathetic towards him although it's clear that she doesn't trust him and even hates him. We don't know if she knows the things that he did against her.

Marita Covarrubias[]

Main article: Marita Covarrubias

Krycek had a relationship with Marita Covarrubias, though the exact nature of it is up to speculation. He met her at the sight of a cosmic event in Russia and argued with her there, ending their seeming disagreement by spitting at her. Shortly thereafter, however, Krycek passionately kissed Marita, while they were alone together. She said to him "We've got them on their knees Alex", insinuating that she and Krycek were in cahoots against the Syndicate. Following this, Krycek was betrayed by her, when she rescued Dmitri from Krycek's captivity. — (Patient X)

He later had an opportunity to rescue a heavily infected Covarrubias from Fort Marlene, but did not take this chance to save her, opting to let her rot in the Syndicate facility — (One Son). Krycek ultimately teamed up with her, upon the pair being dispatched by the CSM to locate and retrieve the Oregon UFO, but instead worked with her to almost fatally injure the CSM. — (Requiem)