Jerry Colangelo, managing director of the U.S. federation, said Rondo had declined the invitation through a phone call from his agent, Bill Duffy, who said Rondo would be unable to attend because of unspecified family commitments.
The development was somewhat of a surprise given that Rondo, after being miffed earlier this year when he was not asked to join the national team, later received an official invitation.
"It's pretty simple, he was not invited originally because we were advised that he was not that interested, then after the fact I was told he very much wanted to, and if he was invited he would absolutely accept, and then came the decision on his part, without any direct contact, that he had chosen not to," said Jerry Colangelo, the team's managing director.
Rondo was not available for comment as the Celtics had the day off following their playoff victory over Cleveland on Monday night.
His agent, Duffy, said "Rajon was honored by the invitation, but he has a family commitment that he made prior to this, and he wants to honor that commitment."
Team USA's roster now stands at 31, including 10 members of the 2008 Olympic team, although several of those players may decline to compete in the World Championship in Turkey in late August and early September.
In the past, Colangelo said players' participation in 2010 will have an impact on whether they are chosen for the 2012 Olympic team. Now, he seems to have softened that stance.
"What happens with the Olympics is we'll cross that bridge when we come to it. This is a new cycle, the last cycle finished in Beijing. This is new cycle and we're just getting off launching pad," Colangelo said.
"One of the great things we've done with infrastructure is there are plenty of people in the pipeline. I'm not concerned about who doesn't go. We'll look at who will be there, and from that group we'll be able to field a competitive team," Colangelo said by phone from Las Vegas, where the U.S. federation formally announced plans for a minicamp July 20-23 and a public scrimmage on July 24.
"It's too early to be specific, conceivably a few from Beijing will not participate. Is it two, five, three? I don't know. We're still in process of finding that out," he said.
With the addition of Evans, the newly-minted rookie of the year, the 31-man roster now includes seven point guards. The others are Chris Paul, Deron Williams, Russell Westbrook, Derrick Rose and Chauncey Billups.
Jason Kidd and Michael Redd are the only members of the 2008 team not currently on the roster, and there is a question of whether free agency will impact the participation of James, Wade, Carlos Boozer and Chris Bosh. Colangelo has previously said that all members of the team will be required to attend the Las Vegas minicamp, although they will not have to participate in the practices.
2004 Olympians Amare Stoudemire and Lamar Odom are among the members of the 31-man roster, which also includes Kobe Bryant, LaMarcus Aldridge, Kevin Durant, Rudy Gay, Eric Gordon, Danny Granger, Andre Iguodala, Al Jefferson, David Lee, Brook Lopez, Kevin Love, O.J. Mayo, Kendrick Perkins and Gerald Wallace.
Duke coach Mike Krzyzewski, along with his assistants since 2006 -- Mike D'Antoni, Nate McMillan, and Jim Boeheim -- have all committed to remaining on the coaching staff through the 2012 Olympics in London.
After the Las Vegas minicamp, Team USA will hold its regular training camp in New York Aug. 9-15 before traveling to Spain and Greece for exhibition games prior to their arrival in Turkey on Aug. 26. The World Championship takes place Aug. 28-Sept. 12.
Chris Sheridan is a basketball writer for ESPN.com.