Whibley married fellow singer Avril Lavigne in 2006. The couple occasionally performed together, and they have spoken about their relationship in interviews. Whibley and Avril Lavigne began dating when she was 19-years old, after being friends since she was 17. Only a few weeks before they met, Lavigne admitted that she was not meeting boys because her bodyguards were frightening them away. In June 2005, Whibley surprised Lavigne with a trip to Venice, including a gondola ride and a romantic picnic, and on June 27, he proposed to her.
She at first wanted to have a "rock n' roll, goth wedding", but she admitted to having doubts about going against tradition. "I've been dreaming about my wedding day since I was a little girl. I have to wear the white dress.... People thought that I would [wear a] black wedding dress, and I would have, but at the same time, I was thinking about the wedding pictures, and I wanted to be in style. I didn't want to be thinking, 20 years later, 'Oh, why did I wear my hair like that?'"
The wedding was held on July 15, 2006. About 110 guests attended the wedding, which was held at a private estate in Montecito, California. Avril, wearing a gown designed by Vera Wang walked down the aisle with her father, Jean-Claude, to Mendelssohn's "Wedding March". Lavigne chose a colour theme of red and white, including red rose petals and centrepieces of distinctly coloured flowers. The wedding included cocktails for an hour before the reception and a sit-down dinner. The song "Iris", by the Goo Goo Dolls, was played during Lavigne and Whibley's first dance.
Seven months into their marriage, Lavigne stated that she was "the best thing that's ever happened to him", and suggested that she helped Whibley stay off drugs since they had begun dating. "He doesn't do drugs. Clearly, he used to, because he talked about it, but I wouldn't be with someone who did, and I made that very clear to him when we first started dating. I've never done cocaine in my life, and I'm proud of that. I am 100 percent against drugs."
The marriage lasted a little more than three years. It was announced on September 17, 2009 that Lavigne and Whibley had split up and that divorce papers would soon follow. On October 9, 2009, Lavigne filed for divorce, releasing the statement, "I am grateful for our time together, and I am grateful and blessed for our remaining friendship." The divorce was finalized on November 16, 2010.
On August 30, 2015, Whibley married model Ariana Cooper in Los Angeles.