Phillips is to perform a version of his American Idol winner's single 'Home' as a tribute to those affected by the recent Joplin, MO and Tuscaloosa, AL tornadoes. Bryan will be singing the National Anthem.
Kellie Pickler will also appear during the seventh inning for a rendition of 'God Bless America'.
The All-Star Game festivities will feature the Zac Brown Band and David Cook as well.
Major League Baseball's 83rd All-Star Game airs on Tuesday (July 10) from 7.30pm ET on Fox.
Watch Luke Bryan's 'Drunk on You' music video below: