Chiles will be joined in the studio by former England defender Gareth Southgate, while Peter Drury and Andy Townsend will on be commentary duties.
The match is Chiles's first outing for the broadcaster since signing a four-year contract earlier this year. His duties include anchoring the channel's World Cup coverage and he will also appear as a main host on GMTV.
The penultimate England warm-up game before the World Cup in South Africa takes place at Wembley. ITV's coverage will kick off at 7.30pm.