Burgess, who has just 70 minutes of Test rugby under his belt since his switch from rugby league, edged out Luther Burrell to earn his spot at inside-cnetre.
The code-hopper ended the club season as a regular in the back-row with Bath after failing to impress in the midfield, but coach Stuart Lancaster has taken a gamble on the 26-year-old.
He will now battle Brad Barritt, Jonathan Joseph and Henry Slade for a spot in England's match-day squad in next month's World Cup opener against Fiji.
Burgess' achievement has been somewhat overshadowed by the omission of enigmatic flyhalf Danny Cipriani who was overlooked in favour of George Ford and Owen Farrell at fly-half, while Mike Brown and Alex Goode have been chosen at full-back.
Jonny May, Jack Nowell and Anthony Watson are given the nod on the wings, but there is no place for hooker Dylan Hartley, who had been linked with a call-up despite being suspended for the opener against Fiji.
"It's really positive that we have such depth and options to choose from," Lancaster said.
"Selection wasn't easy and it is tough to leave anyone out, but it's important to stress that the players not in this group are still part of our wider squad and could come in at any point.
"After 10 weeks in camp we have made our final selection of players and we believe we have a great group to take us into the tournament. With three weeks to go before we play Fiji we believe we are in good shape as we head into next Saturday's game against Ireland.
"As the excitement builds around the tournament we are looking forward to the country getting behind England and we know this group of players will represent the nation with pride."
England face Fiji at Twickenham on September 18, with matches against Australia, Wales and Uruguay to follow in Pool A.
England World Cup squad:
Forwards: Kieran Brookes, Dan Cole, Joe Marler, Mako Vunipola, David Wilson, Jamie George, Rob Webber, Tom Youngs, George Kruis, Joe Launchbury, Courtney Lawes, Geoff Parling, James Haskell, Ben Morgan, Chris Robshaw, Billy Vunipola, Tom Wood.
Backs: Danny Care, Richard Wigglesworth, Ben Youngs, Owen Farrell, George Ford, Brad Barritt, Sam Burgess, Jonathan Joseph, Henry Slade, Mike Brown, Alex Goode, Jonny May, Jack Nowell, Anthony Watson.