The event will also feature the four living ex-presidents: Bush, Bill Clinton, George H.W. Bush and Jimmy Carter. They will appear in a Major League Baseball video recognizing several dozen Americans for their community service.
Whether it's draining a three-pointer for American troops in Kuwait or playing a pick-up game with the North Carolina Tar Heels, Obama has shown he's got game on the basketball court.
But he does not have a long record of exhibiting a natural talent for America's pastime.
In 2005, his first year as a senator from Illinois, Obama, a lefty, threw out a first pitch at a White Sox playoff. The devout Sox fan admitted afterwards that he was feeling the pressure.
"Had I thrown a one-hop, I think, whatever aspirations I had, they would have shown that clip over and over again," he said in an interview with the Springfield State Journal-Register that year.
"I was more nervous than I was before the Democratic National Convention" the year before, he said.
Earlier today, Obama said he wanted to loosen up his arm a bit for the big game and recalled that first pitch in 2005.
"I just wanted to keep it high," he said."Now, there was no clock on it. I don't know how fast it went. But if it exceeded 30 miles per hour, I'd be surprised. But it did clear the plate."
White House aides said the president did not do any practice pitching at the White House but would warm up his arm in St. Louis before the game.
The glove the president used, made by Wilson Sporting Goods with "Obama 44" printed on it, will go to the Baseball Hall of Fame in Cooperstown, N.Y., after the game.
The tradition of presidential first pitches dates back to 1910 when William Taft, not exactly an athlete at over 300 pounds, did the honors from his seat in the bleachers in a game between the Washington Senators and Philadelphia Athletics.
Since then nearly every president has taken their best aim at the catcher's glove.
Obama is the fourth president to throw out a first pitch at the All-Star Game, after John F. Kennedy (1962 in Washington), Richard Nixon (1970 in Cincinnati), and Gerald Ford (1976 in Philadelphia).
George W. Bush, a former co-owner of the Texas Rangers, may have set the gold standard with a perfect ceremonial pitch in 2001.
With New York and the nation still reeling from the Sept. 11 attacks, Bush took to the mound at Yankee Stadium before Game 3 of the World Series between the New York Yankees and the Arizona Diamondbacks.
In the HBO documentary "Nine Innings From Ground Zero," Yankee shortstop Derek Jeter advised the president to not take any shortcuts and throw from the pitching rubber, a major league distance of 60 feet, 6 inches.
Jeter recalled that he had one piece of advice for the president: "Don't bounce it, they'll boo ya."
There would be no "Bronx cheer" that night for Bush, who sent a strike right over the plate. The crowd erupted into chants of "U.S.A., U.S.A."
"The next morning he came in and said to me, no matter what happens in the course of my presidency, that is going to be one of the highlights," former Bush press secretary Ari Fleischer said.
Bush was not always so warmly received, as politics and polling started to creep into the baseball stadium.