Owen Farrell will replace George Ford at fly-half when England face Australia in the first Test on Saturday, while Marland Yarde and Luther Burrell have also been named in the starting line-up.
Farrell played at inside centre during England's successful Six Nations campaign, but returns to number 10 for the opening game of the three-match series against the Wallabies in Brisbane at the expense of Ford, who drops to the bench.
Wing Yarde gets the nod to start ahead of Jack Nowell after an impressive display in the victory over Wales at Twickenham last month.
Burrell was only called up for the tour Down Under when Manu Tuilagi was ruled out due to a hamstring injury, but the centre has been named in the 15 for the eagerly-awaited clash at Suncorp Stadium.
Maro Itoje was tipped to replace Chris Robshaw at blindside flanker, but will continue his lock pairing with Saracens team-mate George Kruis.
Former England captain Robshaw will start at six after playing an influential role in England's Grand Slam triumph, while wing Mike Brown will win his 50th cap.
"We have picked a side to win in Brisbane," said England head coach Eddie Jones. "As always selection was tight and naturally players are disappointed, but we've gone with a 23 that has a good mix of experience and youth.
"We aim to win every Test match we play and I am pleased with our preparation since we landed in Australia. The group have acclimatised well, trained hard and there’s a buzz around the camp."
Centre Samu Kerevi, lock Rory Arnold and wing Dane Haylett-Petty will win their first Australia caps after being named in Michael Cheika's starting line-up.
England: Mike Brown, Anthony Watson, Jonathan Joseph, Luther Burrell, Marland Yarde, Owen Farrell, Ben Youngs; Mako Vunipola, Dylan Hartley, Dan Cole, Maro Itoje, George Kruis, Chris Robshaw, James Haskell, Billy Vunipola.
Replacements: Luke Cowan-Dickie, Matt Mullan, Paul Hill, Joe Launchbury, Courtney Lawes, Danny Care, George Ford, Jack Nowell.