"Everyone who wants to grow up, sooner or later sits down and has a chat with Satan. Or they never grow up."
—Amos Maple, Down From Ten
Before the hero can achieve his destiny, he has to face himself and defeat the darkness in his own heart. Because Only the Worthy May Pass, someone has to put the hero to the test and make sure that he has the character necessary to see things through.
Enter Satan. Sometimes this is the literal Guy With The Horns and Pitchfork (or local equivalent); sometimes it's just the character's Shadow Archetype, or the Old Master. Regardless, it's the character who knows the hero's dark side better than the hero himself — and is determined to make sure the hero sees it, as well.
If the hero fails this Secret Test of Character, expect things to end badly for him.
Essentially, when a supporting character talks to the hero to reveal What You Are in the Dark. Differs from a Deal with the Devil in that the Satan-figure is primarily concerned with exposing the hero's true nature (and can sometimes be akin to a Trickster Mentor, actively trying to improve the hero by getting them to see and reject their darker side); if the hero does not succumb to temptation, it doesn't mean that the tempter has failed in his mission. A type of Threshold Guardian. If the character playing "Satan" really does want to corrupt the hero, then they're The Corrupter.
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Naruto plays this very straight in one example, except for one minor twist; Naruto knows his dark side even better than the "dark side" itself, and actually embraces it and comforts it. In a way, his dark side was something that he mostly outgrew as he grew up.
In Mahou Sensei Negima!, Evangeline goes through this with Negi. She tells him he can either face down his true dark nature and overcome it, bending it to his will, or he can become a raging immortal demon. She thinks the latter is kind of cool.
In Fate/Zero, Kiritsugu has a conversation with the Holy Grail itself, who reveals to him the consequences of his ideology. The revelation is what convinces him that his ideal is actually unattainable, and that the Grail must be destroyed before it sacrifices even more than Kiritsugu was willing to.
In the movie of Haruhi Suzumiya, Kyon is faced by a mirror image of himself (it's all mental) who basically tells him to stop being passive aggressive about his complaining. Either flat say I Just Want to Be Normal and make it happen (he can), or admit that he likes the craziness and STOP WHINING. Now, granted, only the audience is privy to Kyon's unstoppable narrations; so this is Kyon's Id telling him to put up or shut up.
At the climax of Midnight Nation, the villain literally Satan provides one of these for David, challenging everyone from the David himself to all of humanity to God Himself. J. Michael Straczynski really likes this trope, as seen in the examples for Babylon 5 below. He has a degree in psychology and is very aware of ways to constantly press at and tear away people's illusions and justifications until they finally admit to their most selfish and demeaning motivations.
In The Lord of the Rings: The Two Towers, Sméagol talks to his alter-ego Gollum and must choose between his loyalty to Frodo and his lust for the Ring.
In at least two deleted scenes, Aragorn speaks with Sauron. The first time with the Palantír to taunt the Dark Lord with the fact that he now has the Sword of Elendil to which Sauron responds by showing him an image of Arwen dying to break his resolve. The second was an intended battle between the two at the Gates of Mordor. Sauron would have greeted Aragorn by saying "Hail Aragorn, Son of Kings." The second scene was replaced by the Eye of Sauron staring at Aragorn and showing him something... Aragorn replies by charging the gate.
In Serenity, after the death of Shepherd Book, Malcolm Reynolds has a conversation with the Operative who is hunting him. The Operative confronts Mal with the fact that he caused the destruction with his Refusal of the Call. The conversation convinces Mal to put aside his apathy and go on the offensive.
In Silence of the Lambs, Hannibal Lecter plays the Satan to Agent Starling throughout the film. He repeatedly forces her to examine her inner motivations and desires.
In The Empire Strikes Back, Yoda plays this role for Luke when Luke discovers that Han and Leia will be captured by the Empire. Luke must choose whether to "honor what they fight for" by staying to finish his training, knowing that it might mean sacrificing Han and Leia. Luke instead chooses to follow his own reckless impulses and confronts Vader before he is ready. As a result, he loses a hand and has to be rescued by Leia, who has escaped through other means... thanks to R2-D2, who had come with Luke from Dagobah.
As far as confronting his inner darkness goes, Luke's experience in the cave probably counts as well. He attacks the vision of Vader and strikes him down, only to find his own face beneath the helmet; foreshadowing the danger of his reckless choices (like rushing into conflict) and the dilemma he'll face in the next film when he has to confront Vader without giving into the Dark Side (lest he become him).
In Return of the Jedi, the Emperor tries to seduce Luke into joining the Dark Side by confronting him with the darkness inside himself. Luke, in turn, plays an inverted Satan for Darth Vader, confronting him with his own hidden goodness.
The Messenger: The Story of Joan of Arc: Dustin Hoffman plays Joan's conscience made flesh as she awaits execution by the English. He questions her belief in her "vision" and debates with her the righteousness of her mission.
In The Dark Knight the Joker tries this one with Harvey Dent and convinced him to go batshit crazy. He tries it on Batman as well but finally admits that he truly is incorruptible.
In Genesis 3, the serpent tempts Eve with the knowledge of good and evil. His questions reveal that Eve is second-guessing whether God has her best interests at heart.
In Matthew 4, Mark 1 and Luke 4, Jesus goes into the wilderness and is tempted by Satan. The devil presents him with three successive challenges, appealing to his appetite (turn this stone into bread), his vanity (jump off the temple so people will see God catch you), and his sense of his own destiny (worship me and I will give you all the kingdoms of the world). Jesus refuses each of the tests, thus proving that he is worthy to begin his ministry.
Ditto in Buddhism — the last barrier to enlightenment that Siddhartha Gautama faced was Mara, the Anthropomorphic Personification of temptation. Less Demon and more Trickster, Buddha simply touched the Earth to remind him that there was still dirt under his feet and ignored the hallucinations of women that he sent him. Last seen as a giant penis-chariot in Persona 4.
Ivan Karamazov dreams one of these in The Brothers Karamazov. Doubly perturbing for him, as he's a committed skeptic.
In The Dresden Files, Harry has these little chit-chats with alarming regularity. His "inner voice"note Not actually an example of the trope when all is said and done, though, as Harry's inner voice is less evil and more primal: concerned with things such as survival, instinct and so on. It actually has good advice, on occasion, Lea, Lasciel, Nicodemus...
In The Lord of the Rings, Frodo has this chat with Galadriel in Lothlórien, as she probes the purity of his heart around her mirror.
Frodo also plays Satan to Galadriel, tempting her with the offer of the Ring.
In the Betsy the Vampire Queen series by Mary Janice Davidson, Lucifer (in the form of a woman) pops by to have a little chat with Betsy. Lucifer says she looks forward to working with Betsy and please keep an eye on her daughter until she's ready to claim her destiny. Betsy defies her, and she asks if Betsy won't reconsider for a pair of thousand-dollar, one-of-a-kind, mint condition, truly fabulous shoes. Betsy hesitates - and Lucifer smirks, her point made.
Satan: His Psychotherapy and Cure by the Unfortunate Dr. Kassler, JSPS consists largely of backstory and this trope.
Part of the test Gerald has to face in Witches Incorperated (Rogue Agent book 2 by K.E. Mills) to become a Janitor involves a chat with the very dead villain of the first book.
In one of the later Animorphs books, Crayak offers to give Rachel all the power she needs to defeat the Yeerks if she agrees to serve him. This forces Rachel to confront the fact that she's been steadily turning into a Blood Knight over the course of the series.
In The Neverending Story Atreyu has to pass through a mirror gate and face his true self. So does Bastian, the kid reading the book. The latter doesn't take it well.
In H.P. Lovecraft's The Dream-Quest of the Unknown Kadath the protagonist Randolph Carter meets Nyarlathotep, the Crawling Chaos on top of the titular fortress of gods, in the shape of a handsome youth. In this case Carter fails to pass the temptation of the easy path, and almost meets his doom, before finding a loophole in Nyarlathotep's own boasting.
Much of Anne Rice's novel Memnoch the Devil is devoted to Lestat hearing the titular character (who claims to be the devil) retelling (and showing) his own story starting with the creation of the angels and ending with Memnoch turning Sheol into Hell in order to get souls to repent (although that makes Hell sound more like Purgatory) and prove God wrong (i.e. that only those who truly love Him get to be in Heaven).
Battlestar Galactica (Reimagined): Head Six sometimes encourages Baltar toward goodness and sometimes tempts him toward evil, but she usually helps him to come to some important revelation about himself.
Leoben plays this role for Starbuck several times during the series, most dramatically when she is assigned to interrogate him in "Flesh and Bone".
In Season 5 of Supernatural, Lucifer has had talks like this with both Sam and Castiel, but they both resist his seductive nature.
Also in Season 5, Dean had a similar encounter with Death.
LOST: In his flashbacks, Richard Alpert is tempted by the Man in Black/Smoke Monster, who tells him he must kill "the devil," Jacob, if he wants to see his dead wife again. He ultimately refuses and sides with Jacob.
In Ashes to Ashes, Gene Hunt doesn't so much as have a chat with Satan as get audited by Satan, in the form of D&C officer Jim Keats. Apparently, Gene runs this corner of Purgatory (for God, we think), and Keats and his side are kind of pissed that Gene keeps changing the rules. Keats gets in a Reason You Suck Speech against Gene in his opening episode, and they continue to have face-offs whenever Keats wants to remind Gene that Gene isn't fooling him.
In a show as old as Doctor Who, this has definitely happened a few times. In the Classic Series 'Trial of a Time Lord', the Doctor faces his evil future self, and has to resist the temptation of the power the Valeyard has. More recently, the series five episode "Amy's Choice" has the Doctor and his companions trapped in two dream worlds by a manifestation of his darker impulses.
The verse drama Murder in the Cathedral by T. S. Eliot focuses on Archbishop Thomas Becket in the days leading up to his murder. In the first act, he is visited by "tempters" who plead with him to give up his feud with the King of England. The first tempts him with hedonistic pleasures, the second with a restoration of his former authority, the third with political power. He rejects them all, but the fourth tempter surprises Becket by asking him to seek out martyrdom, and be glorified as a saint long after his death. Becket has to reconcile his moral stance with his own selfish desire to be justified in the hereafter. (In most productions, the fourth tempter is presented as being separate, more enticing than the first three, and possibly the Devil in disguise.)
Similarly, Imperium requires you to overcome your inner sin. The relevant splatbook gives a wizardly mentor as an example: the mentor's Satan is his stubborn refusal to acknowledge that other people's methods are probably as good as his, which have costed the life of at least one prospective mage.
In Dead Inside, a Mage who wants to achieve immortality must cut away their Shadow and then either rejoin it or destroy it. The Shadow can provide this chat, and the Mage can reconcile with it as one path to immortality... but most just try to kill the Shadow instead, because they think it'll be easier than swallowing their own pride. (And given how prideful most Mages are...)
In Zelda II: The Adventure of Link, Link must defeat his own shadow, later named Dark Link, in order to obtain the third Triforce piece and awaken Princess Zelda. (However, given Link's status as the world's most legendary Heroic Mime, there's no actual "chatting" involved.)
EarthBound has, as the boss of Magicant, "Ness's Nightmare", which looks exactly like the Mani-Mani statue and rather like the Devil.
Mass Effect 1: Saren counts if you go Renegade, since that's how he operated.
In Baldur's Gate II: Throne of Bhaal, this role is played by an angel. The Solar reveals the player character things about themselves and their destiny bit by bit, and their (the player's) verbal reactions affect a Karma Meter that determines whether, at the end, they become a god of goodness instead of a God of Evil if they choose divinity. Her goal is ostensibly to make the PC understand themselves, but they could go through the whole thing missing the point.
Prince of Persia: The Two Thrones: After defeating the Big Bad, the Prince must face his dark alter-ego in order to regain control of his own body. However, confronting the Dark Prince is not the way to go. The Prince must, instead, walk away. Subverted due to the fact that nothing will happen if you will fight him - you should know this already.
Dragon Age: Origins: While seeking the Urn of Sacred Ashes, the Warden (regardless of his/her origin) will be confronted by the Guardian, a spirit protecting the Urn. The Guardian will pose a personal question relating to the Warden's origin, questioning whether or not the Warden believes he or she failed their friends or family. The Guardian poses similar harsh questions to the Warden's companions. Except Dog.
My Little Pony: Friendship Is Magic: Nightmare Moon does this to Rainbow Dash when she's off alone, attempting to tempt her into forsaking her friends for the chance to live her dream. Rainbow Dash is quick to refuse and help her friends.