Head coach Wayne Bennett has selected the 27-year-old to lead the nation in clashes against New Zealand, Scotland and Australia.
Burgess was included in the 24-man squad on Monday for the first time since the 2013 World Cup.
The South Sydney Rabbitohs player switched to rugby union in 2014, but after a spell with Bath and a failed World Cup campaign with England, Burgess returned to rugby league.
The former Bradford Bulls player will take the captain's armband from Sean O'Loughlin, who will miss the Four Nations tournament due to injury.
"It is an absolute honour and privilege to be asked to captain my country and to lead this group through the Four Nations tournament," said Burgess. "I want to thank Wayne for having the trust and belief that I can do the job and I am determined to do my best for this team.
"Although I am captain on the field for this tournament, there are a group of leaders in this squad and I know that we will work together and as hard as possible to try to achieve success on the pitch for England."
Bennett added: "I know the importance and pride that is placed on being captain of England. In Sam I believe we have got the right guy for the job whilst Sean is injured. He is a player and man who leads from the front and has the utmost respect from his teammates and fellow professionals.
"I know how much it means to Sam to play for his country, he is a huge player across our sport and he knows how to inspire and get the best out of people. I am certain he will do a great job as England captain."
Burgess, who has 16 international caps to his name, will lead England out in their tournament opener against New Zealand on October 29.