England captaincy has come at the right time for hooker George
The 33-year-old hooker, who has previously led Saracens and the British and Irish Lions, succeeds Owen Farrell with his club-mate missing the tournament while he takes a mental health break from international rugby union.
But there is no place in England coach Steve Borthwick's 36-man tournament training squad for the experienced forward duo of Billy Vunipola or Kyle Sinckler.
George has won 85 England caps, plus three for the British and Irish Lions.
"Last week Steve asked me to be captain for the upcoming Six Nations and I accepted with huge gratitude and enthusiasm," George said.
"I love playing rugby for England. I hope that everyone has seen how much it means to me, I have never shied away from that."
He added: "I believe I'm at the stage of my career where I can give my all to the captaincy and give my best on the pitch.
"I don't underestimate the challenge ahead. Owen is a fantastic motivator and tactician, and we will undoubtedly miss his leadership.
"But I have got brilliant people around me, many of whom have won major tournaments, and utilising the great experience we have within the group is going to be crucial."
'Outstanding'
Borthwick, himself a former England captain, explained his decision to appoint George as skipper by telling a Twickenham news conference: "Firstly, I think he's an outstanding player, one of the best hookers in the world, incredible work-rate. Secondly, he's got a fantastic understanding of the game, tactically very astute.
"And thirdly, he's brilliant with people, builds great relationships."
George's appointment was announced less than an hour after Saracens confirmed he'd signed a new two-year deal that will keep him at the north London side - which he joined as a teenager - until at least 2026.
Borthwick was pleased by George's decision, with several players having made themselves ineligible for England by joining overseas clubs.
"It's a real positive step and maybe a sign that English rugby has turned a corner," said Borthwick, with several clubs in England's top-flight Premiership having gone out of business last season.
Only half of the squad that finished third at last year's World Cup in France have been retained.
Centre Henry Slade and hooker Luke Cowan-Dickie, who both missed out on the World Cup, are recalled.
Scrum-half Ben Spencer, last capped by England during their 2019 World Cup final loss to South Africa, also returns after starring for Bath.
Uncapped Exeter wing Immanuel Feyi-Waboso, born and brought up in Cardiff, is one of seven uncapped players in the squad.
Fellow wings Oscar Beard and Tom Roebuck, back rows Chandler Cunningham-South and Ethan Roots, centre Fraser Dingwall and fly-half Fin Smith are the other squad members yet to make a Test debut.
England have won just two matches in each of the past three Six Nations, a record Borthwick, who took over from the sacked Eddie Jones before last year's edition, is determined to improve.
"In the last six years we've won 50 percent of our games in the Six Nations and that's something we need to improve," said Borthwick.
"It's a really competitive competition. I think we've built some foundations over this last period of time and what we need to do is build and grow on that."