The faculty and students of Sheffield Institute.
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Faculty
Ms. Knickerbocker
Voiced by: Candi Milo
The principal of Sheffield.
- British Stuffiness: The cartoon gives her a British accent.
- Butt-Monkey: She sometimes becomes this due to the actions of the girls.
Dean Collins
Voiced by: Cam Clarke
The history teacher of Sheffield.
- Bad "Bad Acting": Noted on it by Will in the cartoon's second season episode, "J is for Jewel".
- Brainy Brunette: He has brown hair and is the History teacher at Sheffield Institute.
- Butt-Monkey: Unfortunately becomes this when W.I.T.C.H. thinks that he was the spy sent to Earth from Cedric in the cartoon.
- Took a Level in Badass: In the second season episode, "M is for Mercy", Dean manages to pull Susan up to safety...using just one arm and sheer will.
Students
Nigel Ashcroft
Voiced by: Michael Reisz
Taranee's love interest and later boyfriend.
- Adaptational Nice Guy: He is introduced in the show as a former bad boy who becomes Taranee's love interest. In the comics, he starts off as a member of Uriah's gang and partakes in bullying up until his Heel–Face Turn.
- Catchphrase: "Sweet!"
- Deadpan Snarker: Has shown to deal a lot of sarcasm.
- Remember the New Guy?: When he's introduced in the show, it's mentioned he used to hang out with Uriah's gang, but this was never seen, unlike the comics where he was part of the gang from the start.
Eric Lyndon
Voiced by: Justin Shenkarow
Hay Lin's love interest, and later, boyfriend.
- Chick Magnet: "L is for Loser" shows two cheerleaders practically fighting over him.
- Curtains Match the Windows: In the cartoon Eric has blue eyes and blue hair.
Martin Tubbs
Voiced by: Dee Bradley Baker
A friend of W.I.T.C.H. who has a crush on Irma.
- Fiery Redhead: Downplayed, as Martin is more outgoing than "fiery".
- Hopeless Suitor: He has had a crush on Irma since they were kids but she's only seen him as a friend.
Alchemy
Voiced by: Lauren Tom
A friend of the girls at Sheffield Institute. She is around the same age as the girls, and is wholly ignorant of what Elyon and W.I.T.C.H. do.
- Canon Foreigner: She never appeared in the comics.
- Childhood Friends: With Cornelia and Elyon.
- Crush Blush: Towards Caleb in the cartoon's first season.
- Nice Girl: Was so worried about Elyon being missing that she convinced Principal Knickerbocker to call the police. That's true friendship.
- One Name Only: Alchemy's surname is never revealed. There is a fan theory that her surname is Ethel due to a throwaway line in the episode "Divide and Conquer", but this was never confirmed and the Ethel in question was never implied to be Alchemy in the first place.