Episode 1X04: The Jersey Devil: Scully catches Mulder reading a pornography magazine at the start.
Episode 2X03: Blood: Mulder sheepishly admits to the Lone Gunmen that he didn't read one issue of their magazine because it arrived the same day as his subscription to Celebrity Skin.
Episode 2X07: 3: Mulder has a swimsuit calendar in his office (though strangely, he apparently didn't take it home with him when the X-Files are shut down).
Episode 2X08: One Breath: Mulder is quite possibly watching a porn movie on TV before learning that Scully has been found.
Episode 2X11: Excelsis Dei: Mulder arrives in the office to see Scully watching Nurse Charters' video and thinks she's discovered his secret porn collection.
Episode 3X02: Paper Clip: Mulder tells Frohike he can't have his video collection yet, which is implicitly the same video collection mentioned in Episode 2X11: Excelsis Dei. Mulder has called Frohike a pervert in previous episodes.
Episode 3X03: DPO: Mulder discovers Darren Oswald's porn magazine and Scully comments she'd have thought he had that issue.
Episode 3X04: Clyde Bruckman's Final Repose: Not exactly a porn reference, but Clyde Bruckman hints that Mulder will die from autoerotic asphyxiation.
Episode 3X17: Pusher: Mulder asks if his mini camera can pick up the Playboy Channel.
Episode 5X17: All Souls: Mulder pretends he's tailing a suspect when actually he's waiting outside a cinema with a number of Xs clearly visible behind him. When he steps out of the phone booth and runs to the cinema, it is confirmed that he was just out to watch porn; the sign on the cinema reads: "A DECADE OF DIRTY DELINQUENTS".
Episode 6ABX04: Dreamland: One of the most obvious references yet; Joanne Fletcher catches "Morris" (actually Mulder) sleeping in front of a porn channel twice.
Episode 6ABX05: Dreamland II: When Morris discovers Mulder's bedroom, he finds it piled high with junk. At least one of the items is a porn magazine.
Episode 8ABX08: Per Manum: Mulder makes an implicit reference to "pleasuring" himself in this one, when Scully talks about the tests to see if he is a suitable sperm donor; he makes a remark about being an expert.
Not on the X-Files, but Millennium's Frank Black apparently also has a porn addiction. In Episode 5X12: Luminary, we discover that he has a file on his computer entitled: Ladies of the Night.
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