I just read this article on tv line and got super excited!!!!!

The CW's Supernatural aims to slay you by reuniting Buffyverse alumni Charisma Carpenter and James Marsters — aka Cordelia and Spike — in one of its Season 7 episodes, TVLine has learned exclusively.

What's more, the two actors, who previously worked together both on Buffy the Vampire Slayer and its David Boreanaz-fronted spin-off Angel, will be playing husband and wife on the spooktacular drama, which launches its new cycle on Friday, Sept. 23, at 9/8c. Watch for this glorious genre-gasm to come in the new season's fifth episode, titled "Shut Up, Dr. Phil."

Isn't awesome? ^_^
I read somewhere (think it was tumblr) that Charisma's character is supposed to be a witch who's angry at her husband (James' character) and takes it out on the town.