The Coldplay frontman left his spouse blushing and covering her face with her hands when he ran through the audience to show his affection for the actress between songs at the American Airlines Arena in Miami, Florida.
The kiss was caught on video by a fan and shows Gwyneth, despite her embarrassment, was clearly delighted by the unexpected gesture from her husband.
Later in the evening, Chris - who is rarely pictured in public with the `Iron Man` star - dedicated `Yellow` to his "incredible wife Gwyneth".
Following the concert, the couple - who have children Apple, eight, and six-year-old Moses - were seen looking "so much in love" at the LIV at Fontainebleau Resort venue.
A source told People: "Chris and Gwyneth drank champagne and she was all over him. They looked so much in love. Gwyneth danced all night."
Chris and Gwyneth married in December 2003 and were last seen sharing a kiss in public earlier that year.
The pair are usually based in London, England, but recently splashed out $10 million on an estate in Los Angeles.