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When did Buffy and Spike come face to face for the first time?

School Hard. Spike came to Sunnydale to revive Drusilla.

When did Buffy kill Angel?

Becoming Part 2. Buffy had to kill Angel to stop Acathla from sucking the world into Hell.

When did Anya first make known that she had a thing for Xander?

The Prom. Anya asked Xander to the prom baceause he was the only guy she could stand... that, and she really wanted to go.

When did Willow admit that she loved Tara?

New Moon Rising. Willow chose Tara over Oz.

When was Dawn first mentioned on the series?

Graduation Day Part 2. From the season five featurette, "Spotlight on Dawn": David Fury: "Dawn was introduced as an idea way back in the third season. Faith in the last episode of the third season -"Graduation Day part 2" - in a dream that Buffy had, or possibly a shared dream between Buffy and Faith - Faith referenced 'Little Miss Muffet'." (Faith: "Miles to go, Little Miss Muffet counting down from 730".) Joss Whedon (same featurette): "We had set it up in the end of season 3 with Faith saying, you know, 'counting down from 730' which is 2 years exactly by the day. And that was my was of saying obviously that 'Little Miss Muffet' was Dawn." Of course in a different interview Joss Whedon claimed that 730 was the countdown to Buffy's death, but "little Miss Muffet" was Dawn. In "Real Me" the crazy man told Dawn she was "curds and whey" - a direction link to the Miss Muffet reference.

Spike searches for a mythical demon and fights for his life to win a soul for Buffy in all of the following episodes except which?

Seeing Red. Spike left to get what Buffy deserved and returned with a soul.

Riley stakes Spike.

Into The Woods. Riley staked Spike with a fake stake (hey, that rhymes!) to prove to Spike that he's not afraid to kill him. (So, uh, why did he use a fake stake? I'm not complaining, just wondering.)

Faith realizes that she has a problem and asks for help.

None of these. Faith actually did this in the "Angel" episode "Sanctuary."

When does Buffy realize that she could defeat The First?

Chosen. The First reminds Buffy about the rules of Slayer-hood: there is only one slayer. So Buffy breaks the rules.

When does Spike live the "best night of his life"?

Touched. All he did was hold Buffy while she slept.