4. Stannis Baratheon and Melisandre - Season 2 Episode 2:
Stannis is a noted warrior and as the oldest brother to the departed King Robert Baratheon, he is the rightful successor to the throne (as Joffrey is not a true Baratheon). But it is the priestess of R'hllor and Shadowbinder (follower of the Lord of Light), Melisandre, who urges him to lead his men into battle to claim the throne. In one of her manipulative moments with him, she seduces him into betraying his sickly wife and having sex with her. And though the premise isn't great, neither character is particularly likable and he isn't particularly attractive, the scene is hot, in part because he goes so quickly from standing his moral ground to giving into her advances wholly and hungrily.
It's not sex based on love or passion. It's a bit more primal and practical than that, but the sense of urgency and suddenness make it steamy. And the fact that they do it on top of a table set up as a map of Westeros and the camera focuses on pieces representing different people/groups as they fall to the floor and break give it an ominous tone that intensifies the scene as a whole.
Watch the scene here from 10:01-10:36.
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