The Italian striker gained his spot by winning the AT&T 'In the Game' Challenge, where video gamers from around the world voted by playing FIFA 13.
Fans around the world scored 73,838 goals with Di Vaio through the FIFA Soccer 13 video game over a week-long period ending Wednesday, securing the Impact striker's place among the Fan XI.
"I am very proud and honored to be the first ever player selected to the MLS All-Star team by the millions of FIFA Soccer 13 players around the world,” Di Vaio said in a press release.” I would like to thank all those fans around the world who played FIFA 13. I am proud to represent the Montreal Impact as an MLS All-Star."
Di Vaio outscored 26 other eligible MLS forwards in the video game challenge, with one goal equaling one vote. Los Angeles Galaxy striker Robbie Keane place second, with fans scoring nearly 70,000 times with the Irishman in the video game.
In total, gamers scored over 488,000 goals with the eligible forwards over the week-long competition.
With the Fan XI set, the game day roster will be named by Sporting Kansas City and MLS All-Star head coach Peter Vermes on July 15. Vermes will guide the league's stars against AS Roma at the 2013 MLS All-Star Game on July 31 at Sporting Park in Kansas City.