Charisma Carpenter

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.”

“This episode is ‘Bewitched gone wrong,’” reveals showrunner Sera Gamble. “[It was] all upside for this successful man (Marsters) while he was married to the witch (Carpenter), but now that he’s pissed her off, the whole town is paying the price.”

TVLine happened to be speaking with Carpenter on Wednesday morning (to talk up her Sept. 1 Burn Notice appearance), when she shared what little she could about her Supernatural outing. “My people called me yesterday to see if I wanted to do it and I’m like, ‘Yeah, I’d love to go to Vancouver in the summer!’” she said. “It’s probably one of my all-time favorite cities.”

At the time, little did Carpenter know that the Canadian seaport would be playing host to the biggest on-screen Buffy reunion to date, or at least since her and Nicholas Brendon’s 2006 ABC Family movie, Relative Chaos.

Carpenter and Marsters will film their Supernatural appearance the week of August 22 — after the former swings by New Orleans for a cameo in Haunted High, a just-announced Syfy original movie about teens trapped in a school by the ghost of a headmaster (played by Lost‘s M.C. Gainey). Pulp film icon Danny Trejo (Machete) costars as a possible hero, while Carpenter lords over the school’s library.

“I asked the director, ‘Can I be totally unrecognizable, using make-up effects, or do I have to be a ‘hot’ librarian?’ And he was like, ‘Hot. Librarian,’” she relates with a laugh. “For once, I want to be something different!”

Carpenter was just seen pulling “double” duty this past Monday on Lifetime’s Deadly Sibling Rivalry (encoring Saturday at 9/8c), while Marsters’ most recent TV credits include Hawaii Five-0, Smallville and Caprica.