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Stella & Ben, The Fall
When Stella gives her hotel room number to Ben, it's one of the most straight-forward pick-ups by a female character on TV. Ever.
Don & Rachel, Mad Men
Don Draper had a lot of affairs, but his love for married store owner Rachel Katz was the hottest, deepest, and realest relationship he seemed to get into.
Lip & Helene, Shameless
Lip's forbidden affair with his older female professor created some of his hottest scenes on the series to date -- in part because he finally got emotionally invested in his sex life.
Henry & Casey, Party Down
The sexual tension between these two finally came to a head when Casey told Henry she was getting a divorce.