The Shark Night 3D star will play Billy, a former love interest of Faye (Phoebe Tonkin), according to Entertainment Weekly.
When Billy returns to town and shows an interest in the popular Cassie (Britt Robertson), secret witch Faye will begin plotting her revenge.
"Faye will be a force to be reckoned with," explained executive producer Kevin Williamson. "You'll love to hate her, and you can't wait to see what she does next."
Zylka previously starred in the television version of 10 Things I Hate About You and has appeared in episodes of 90210 and Cougar Town.
He will also play the role of high school bully Flash Thompson in Marc Webb's The Amazing Spider-Man, due for release in July 2012.
Dexter's Adam Harrington, Heroes actress Ashley Crow and Species star Natasha Henstridge have also signed up for roles in The Secret Circle.
The fantasy series premieres on September 15 on The CW.
> Thomas Dekker teases Secret Circle role
Watch a preview of The Secret Circle below: