Chase, 39, will step into the role of Bryan McKenzie, a Sterling-Bosch vice president whom Sara (Hilarie Burton) suspects of stealing a Stradivarius. Bryan is described as highly ambitious with a special interest and appreciation for Chinese culture.
Both actors will appear in the episode "Pulling Strings," which is set to air when White Collar returns for the final six episodes of Season 3 in January.
Skerritt, an Emmy winner for his performance on Picket Fences, recently played the father of Timothy Hutton's character on Leverage. Chase, best known for his work on Buffy the Vampire Slayer and Saving Grace, can be seen these days on Damages.
White Collar airs Tuesdays at 9/8c on USA.