Jones had been a candidate to be voted onto the team by fans in baseball's Final Vote campaign. Instead, Jones, 40, is replacing Kemp, who is on the disabled list with a hamstring injury but plans to participate in the All-Star Home Run Derby.
Jones said he immediately thought about his children when he was told by general manager Frank Wren of the honor after batting practice on Tuesday.
"I'm gonna be a kid in a candy store carrying four other kids in a candy store," Jones said.
He said his spot on the All-Star team "was a complete surprise."
The All-Star Game will be played at Kansas City's Kauffman Stadium. Jones said it is the only current stadium in the major leagues in which he has not played.
Jones will be making his eighth All-Star appearance in his final season. He has announced plans to retire after the season.
He is hitting .291 with six homers and 29 RBIs. He said he will tell NL manager Tony La Russa he would be happy just to watch if he is not needed in next Tuesday's game.
Jones will join Braves teammates Dan Uggla, the starting second baseman, and closer Craig Kimbrel on the NL team. Center fielder Michael Bourn remains a candidate in the fans' Final Vote for the last roster spot.
Jones was injured and did not play when he was named to the 2011 All-Star team. He is 5 for 13, for a .385 average, with one homer in six All-Star Games. He started in 2008.
"I've felt the same excitement every time," Jones said.
Jones' 460 career homers are No. 3 on the list of switch-hitters, behind Mickey Mantle (536) and Eddie Murray (504).
He entered Tuesday night's game with a season-best nine-game hitting streak. He said he has regained confidence in his swing after missing two weeks with a contusion on his left leg.