The song was released as the fourth and final single from their self-titled second album, Jonas Brothers, on December 28, 2007.

The song was released as the first single on the band's third album A Little Bit Longer in Japan, re-titled in Japanese as "Mitsumeau Koi" (見つめあう恋, "Love Is Watching Each Other").

"When You Look Me in the Eyes" "avoids wallowing in cliche by featuring the ever-present youthful energy of Nick and Joe Jonas sharing vocals.

It shows the Jonas Brothers playing the song during a concert and footage of their personal lives.

Most of the music video was filmed inside The Eagles Club (The Rave) or outside in downtown Milwaukee, Wisconsin and in the Chicago, Illinois area.