"That's my goal," James told reporters at a packed press conference on Friday. "I accomplished one and hopefully can accomplish the gold medal as well."
"It's been a great year to this point. I've got an opportunity to accomplish a lot of things and make this year one of the best years of my life."
The U.S. basketball team are huge favourites to prevail in London despite a tournament with talented teams including 2008 silver medallists Spain while rosters for Argentina, Brazil and France also feature NBA talent.
The Americans launch defence of their 2008 Beijing title on Sunday against a French team featuring San Antonio Spurs guard Tony Parker.
James had a difficult transition two seasons ago after leaving the Cleveland Cavaliers as a free agent to form a "Big Three" with Dywane Wade and Chris Bosh in Miami.
They were treated as villains in NBA arenas, where opposing fans jeered them, hoping to see the loaded Miami Heat fail. James fell short of winning his first NBA title when the Heat lost to the Dallas Mavericks and Dirk Nowitzki in the finals.
After a summer working on his game, James emerged as a more complete player and led Miami to a five-game title victory over Oklahoma City in the finals and was named MVP of the series.
"I'm never satisfied. I try to get better each and every off-season," he said.
"I'm not satisfied with just having one ring. Hopefully, I can get another gold medal and that would be two, and hopefully I can continue to compete at a high level and compete for more championships."
The U.S. team are blessed with great depth and diversity, although a lack of towering height in the frontcourt has made it something of a non-traditional team, relying on the 6-foot-8 (2.03 m) James to be defend much taller players.
"Height is overrated," said James, whose strength always him to match-up with taller opponents. "It's not how tall you are, how fast you are or how quick you are.
"It's about what's inside," he said, pointing to his heart. "Height doesn't mean anything."
Capable of playing a suffocating brand of defence, the U.S. team might put on a fastbreak demonstration on the Olympic stage, turning steals into breakaway dunks.
"Will we put on a show?" pondered James. "We are here to have a good time. You should have a good time doing what you love to do.
"If our game translates into our fans appreciating, then we like that. But we don't go out there saying let's put on a show. We just hope that the way we play the game will automatically take care of that."