In 2010, Phillips had his first All-Star season. He finished the season batting .275, with 18 homers, 59 RBI, and 16 stolen bases.
On November 10, 2010, it was announced that Phillips had won the second Gold Glove of his Major League career.
The 86th All-Star Game was played at Great American Ball Park, and Cardinals catcher Yadier Molina was selected to play. In the Reds' clubhouse for the All-Star Game, he was assigned Phillips' locker. Since the brawl between the Cardinals and Reds in 2010, the two mended their schism, and Molina has a photograph of their families together. When informed of whose locker he was using, he replied, "This is Phillips' locker? How about that? I'll have to write something to him." However, during pregame roster introductions, Reds fans booed all six Cardinals players in jest who were selected, including Molina, and even former Cardinal Albert Pujols, who was then with the Los Angeles Angels of Anaheim. Phillips finished the season hitting .294 (16th in the National League) with 173 hits (8th in the NL), 12 home runs, 70 RBI, and 23 stolen bases (10th in the NL).