Biden will join the previously announced guests, Uber Chief Executive Officer Travis Kalanick and country singer Toby Keith, on the program.
He became the 47th veep of the United States in 2009 and is currently serving his second term with President Barack Obama. Previously, he served 36 years as a U.S. Senator from Delaware.
Colbert, former star of The Colbert Report, is taking over The Late Show from longtime host David Letterman, who retired in May after more than three decades in late-night television. Colbert's first show will air Sept. 8.