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"Smoke Gets In Your Eyes" (Season 1, Episode 1)
Why it's great: Matthew Weiner spent years trying to get the "Mad Men" pilot made. His patience was worth it. This is a fantastic introduction to Don Draper and the world he inhabits — including his present mistress, his future one, his wife, his new secretary (and future protege) and many of his co-workers — even as it's also giving us young Peggy's very different perspective on life at Sterling Cooper. We get our first improvised Don Draper pitch, as he coins "It's Toasted" in a meeting with the Lucky Strike execs, the start of the Peggy/Pete affair (as well as the first signs of Pete's jealousy towards Don), and our first sense of the show's deep artistic ambitions. That Don has a wife waiting for him at home felt like more of a cliche than it might have had someone produced the script when Weiner originally wrote it, but everything else is perfect.
Best line: Don tells Rachel Menken, "What you call 'love' was invented by guys like me to sell nylons."