The Italian, who is fondly remembered by Blues fans for two FA Cup final goals, discovered his Baggies side will travel to Chelsea when the Blues open the defence of their title on August 14.
"It's certainly a challenging start," Di Matteo said on West Brom's official website. "But having the chance to play at grounds like Stamford Bridge, Anfield, the Emirates Stadium and Old Trafford is exactly what we battled so hard for last season.
"It will be the coaching staff's job to get the players as best prepared as possible for the challenges that lie ahead. We'll certainly need to hit the ground running as opening fixtures don't come much tougher than Chelsea away.
"They finished last season with an 8-0 win and have got top quality throughout their squad but we will go there with a plan with a view to giving them a real game.
"Of course, going back to Stamford Bridge will be a special occasion but we will all be fully focused on one thing - getting a result for Albion."