The Dutch musician will appear in an ad campaign and create a limited-edition capsule collection for the brand. He will represent Guess at his performances by wearing the label, reports ELLE.
Tiesto is set to debut a Guess watch in August, followed by men's and women's clothing lines in October.
He said in a statement: "I've been a fan of the brand for a long time. It's really an honour to have been selected to partner with them in such a global way. The opportunity to work with Paul Marciano and his company is truly invaluable as I continue to build my clothing brand CLVB LIFE."
Marciano, the brand's CEO and creative director, called Tiesto the perfect choice "to represent the free-spirited, adventurous and sexy Guess lifestyle".
Tiesto has worked with several artists in the music industry, including Britney Spears and Nelly Furtado and fellow DJs and producers Calvin Harris and Diplo.
Last month, he spoke to Digital Spy about his career, which has spanned 18 years.
"I don't know what the secret is, but I just do my thing," he shared. "I didn't even promote myself during the voting for that poll, so it's an honour that people appreciate my music. I think the secret is that fans know I'm real and see that I'm in the music business for the right reasons."
Watch a promo video for Tiesto's 'Club Life College Invasion Tour' 2012 below: