And Buffy spin-off character Angel, the vampire with a soul, was rated ninth in the league.
Laurie Anderson will also perform, as will Buffy Sainte-Marie and Berlin-based art band Tenderloin.
With a name like Buffy, the Facebook phone's mission is clear: slay all comers.
But Buffy creator Joss Whedon is planning a spin-off which may include some original cast members.
The second half is more tongue in cheek, closer to "Buffy" than the Brontes.
Except for Joss Whedon, 45, creator of cult TV hits like Buffy the Vampire Slayer, Angel and Firefly.
Dallas and Dynasty produced Knots Landing and The Colbys, and Buffy spawned Angel.
There have been constant rumours in recent years that Buffy would be axed.
Last season Bebe (pronounced BEE-bee) nabbed Sarah Michelle Gellar, star of Buffy the Vampire Slayer and idol of American teenage girls.
Buffy is shown on Sky One and BBC Two in the UK, while Angel is screened by Sky One and Channel 4.
"I still cannot get over the fact that Shain Gandee died he was my favorite, " tweeted one fan named Buffy Sue.
Gellar, who is married to actor Freddie Prinze Jr, said she was keen for Buffy to end while it was still popular.
Whedon, as you remember, is the auteur behind Buffy the Vampire Slayer.
The 25-year-old has forged a career away from Buffy, starring in the blockbusters including I Know What You Did Last Summer and Scooby-Doo.
He describes it as Lord of the Rings meets Buffy the Vampire Slayer meets The Muppets, with a little bit of Stars Wars thrown in.
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Mr Moonves said Buffy star Gellar had yet to make a decision on whether she wanted to quit her role as the Californian vampire slayer.
"Buffy, in this incarnation, is over, " Gellar told Entertainment Weekly magazine.
"Buffy slays Cubs, " blared the headline in the rival Chicago Sun-Times.
Along with Bryan Singer producing, the cast includes Alexis Denisof (Buffy the Vampire Slayer), David Clayton Rogers (Jane by Design), Sean Gunn (Gilmore Girls).
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To modern eyes, the scythe may be best known from images of the Grim Reaper and Father Time--or as a weapon used by Buffy the Vampire Slayer.
Sky One is the home of American imports such as Buffy the Vampire Slayer and The Simpsons, where episodes can usually seen first before airing on terrestrial channels.
But so did Tricia Helfer and Mary McDonnell during their run in Battlestar Galactica, as well as Sarah Michelle Gellar and Anthony Stewart Head in Buffy the Vampire Slayer.
There will be a return of many favourite characters from the past as it reaches its climax including rogue slayer Faith and Buffy's first love Angel, played by David Boreanez.
Jennifer Love Hewitt ("Can't Hardly Wait"), Sarah Michelle Gellar of Fox's "Buffy the Vampire Slayer, " David Spade (NBC's "Just Shoot Me") and martial arts movie star Jackie Chan were on the list.
TVSquad's Ryan Budke lists his favorite five Simpsons Treehouse of Horror segments and Keith McDuffee rattles off his list of the best five episodes of Buffy the Vampire Slayer.
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The Avengers, which sees a team of Marvel comic-book heroes team up to fight an extra-terrestrial threat, was directed and co-written by Joss Whedon, creator of the TV series Buffy The Vampire Slayer.
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For Milly Williamson, author of The Lure of the Vampire: Gender, Fiction and Fandom from Bram Stoker to Buffy the Vampire Slayer, the changing cultural depictions of vampires reveals much about human society itself.
Dollhouse, helmed by Buffy the Vampire Slayer's Joss Wheedon, will be joined by two more animated series (another signature of the young-skewing network): Family Guy-spinoff Cleveland and Mitch Hurwitz's Sit Down and Shut Up.
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