The 36-year-old, who retired from playing in May last year, has teamed up with O2's Wear the Rose campaign ahead of the World Cup, which will be hosted by England in September.
As part of his role in the O2 Touch Tour, the 2003 World Cup winner will provide rugby-themed mentoring to unemployed people aged from 16 to 24, who will learn employability skills through rugby.
"I'm thrilled to be joining O2 and supporting their 2015 plans," Wilkinson said in a statement. "We're working on inspiring the nation to get behind England Rugby.
"We'll be touring the country, offering support and guidance to young people by showcasing what rugby can do and creating exclusive rugby experiences for O2 customers - it's fantastic to be involved."
The World Cup will get underway on September 18.