The announcement was made by new England head coach Wayne Bennett at a press conference at the team's hotel in London.
The 27-year-old South Sydney forward has been chosen, ahead of former St Helens prop James Graham, as the successor to Wigan loose forward Sean O'Loughlin, who was last week ruled out of the Ladbrokes Four Nations Series through injury.
"Sam will be our captain," Bennett said. "He leads from the front."
Graham is set to lead England in Saturday's international against France in Avignon because Burgess still has to serve a one-match ban carried over from the NRL season, but he will be back to captain his country for the first time in their opening Four Nations clash with New Zealand at Huddersfield a week later.
Burgess, who led Souths this year when Greg Inglis was absent through injury or representative duty, has long been touted as a future England captain and, after being used as the face of the Four Nations in the RFL's poster campaign, will provide them with a public relations coup.
The appointment of Burgess, who is joined in England's 24-man squad by his twin brothers George and Tom, comes less than 12 months since he returned to rugby league following an ill-fated spell in rugby union.
Burgess, a big-money buy for Bath, spent just 11 months in the 15-man code but won five caps for England under Stuart Lancaster before cutting short his stay and returning to Souths on a three-year deal.
He becomes the seventh captain of the national side in the last decade, during which time Australia have had just two men in charge.
Since Andy Farrell quit as Great Britain skipper in 2004 to switch codes, the job has been held by Paul Sculthorpe, Adrian Morley, Graham (in a temporary capacity), Jamie Peacock and Kevin Sinfield until O'Loughlin - Farrell's brother-in-law - was appointed by Steve McNamara two years ago.
Melbourne and Queensland hooker Cameron Smith, who succeeded Darren Lockyer as Kangaroos skipper in 2012, won his 45th cap in Saturday's 26-6 win over New Zealand in Perth and is showing no signs of slowing up.Reuse content