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Hey, It's That Guy!:
Amy Acker will forever be known as Winifred Burkle. Or, depending on your flavor of Whedon, Dr. Saunders.
Anna Espinosa ( Gina Torres) would later turn good and become Zoe Washburne.
Weiss became Matt Parkman and was in BASEketball! Also, Sark became Adam Munroe, Josef Bazhaev, and Uncle John Gilbert!
One of the biggest has been Bradley Cooper, who played Will Tippin and is now a bonafide "movie star" ( Wedding Crashers, The Hangover, and the remake of ).
The A-Team Jack Bristow was sorry he couldn't build a better ship for Kate Winslet, and was Clown Superman in suspenders.
Vaughn gave Drew Barrymore her first kiss
Ariana Kane, head of Counterintelligence for the Alliance was once a famous criminal
Edward Poole, head of SD-9 once had a license to kill (yep, Roger Moore)
Martin Shepard, an amnesiac assassin once fought Mummies with Brendan Fraser
F.B.I. Assistant Director Kendall would end up on a wheelchair and stranded on an Island. (He was also the Chairman of the Joint Chiefs.)
And Kelly Peyton once worked for a badass vampire with a soul and became the vessel for an Eldritch Abomination.
Arvin Sloane turned into a winery owner.
McKenas Cole and Dr. Brezzel moonlight directing movies.
Kate Beckett worked as a stewardess briefly.
What Could Have Been: Roger Moore's role as Edward Poole was originally planned to be recurring, but Moore and the producers couldn't agree on his salary so the character was killed offscreen a couple episodes after his first appearance.