Dueting with girlfriend Katy Perry on the track, which they cowrote for his latest album, Paradise Valley, the couple posed for professional portraits to accompany the release.
"I'm excited to give you the first look at the single artwork for 'Who You Love,' shot by the great Mario Sorrenti," Mayer, 36, writes in a post on his Tumblr. "Get it at the iTunes Store, and then head over to Vanity Fair to see exclusive photos from the shoot."
"And yes, we look like this at home pretty much all the time," the musician jokingly adds.
Debuting the cover shot on his Instagram, Mayer captioned the image, "Proud of this song, proud of this artwork, proud of this girl."
The pair, who began dating in the summer of 2012 before breaking up and getting back together, are featured in four additional shots on VanityFair.com.
Mayer wraps his U.S. tour later this month before heading to Australia in April, while Perry kicks off her 2014 world tour in support of Prism early next year.
Hit play to listen to "Who You Love" below.