The sponsorship will last over two years and will appear on the front of Wolves' shirts next season.
Wolves and controversial former shirt sponsor The Money Shop had mutually agreed to exercise the break clause in their three-year deal this summer.
Managing director Laurie Dalrymple said: "We are delighted to confirm W88 as our shirt sponsor for Wolves’ first season back in the Premier League and we are thoroughly looking forward to working with them moving forwards.
“The commitment they have shown Wolves even extends to them allowing their logo to be changed to black and grey to complement our old gold, rather than their brand’s usual blue colour, something which we are very grateful for.
“This partnership is certainly the largest in the club’s history, and we are looking forward to working with W88 over the next two seasons.”
The W88 logo will also feature on Wolves' full range of training wear, which will be released alongside the new home kit later this month.
Hilly Ehrlich, business development manager of W88, said: "We are absolutely thrilled to partner Wolves, a respected football club with a rich sporting heritage that has helped to shape modern football today.
“This partnership is a major step for us in expanding our global footprint and we look forward to working with the club to engage the fans and supporters of Wolves, both in the UK and worldwide."