Photos show the royal dabbing her cheek with a tissue as the couple emerged from Sainte Devote church following their religious ceremony at the Prince's Palace of Monaco.
The South African swimmer later opened up about why she was emotional, shutting down rumours that it was associated with Albert's infidelity.
WATCH: Princess Charlene and Prince Albert share touching video ahead of tenth wedding anniversary
Speaking of her big day, Charlene said in an interview with The Times: "Everything was just so overwhelming and there were all the mixed emotions because of the rumours, and obviously the tension built up and I burst into tears [immediately after the ceremony].
"And then I burst into tears some more because I was thinking "Oh no, now the whole world has seen me cry"'.
The royal admitted to feeling "overwhelmed" on her wedding day
She went on to add: "It was such a wonderful three days. Even months afterwards I would get flashbacks and think, 'Oh, my goodness, did I really have the Eagles playing at my wedding?' I think back and wonder how we managed to pull it off."
The gorgeous three-day wedding celebrations began with a concert on 30 June 2011 by classic rockers the Eagles and ended with a lavish reception on 2 July attended by the guests, who ranged from the Monaco royal family to Prince Edward, his wife Sophie, and Naomi Campbell.
The couple got married in 2011
Charlene's close friend and maid of honour Isabella Kristensen told HELLO!: "It was absolutely beautiful. Albert's speech was touching, Charlene's father’s speech was amazing. Everyone found the whole event to be very romantic. Charlene moved to Monaco for love, and this was special."
The couple celebrated their tenth anniversary this year but were forced to spend it apart after Charlene contracted a severe ear, nose and throat infection in May, meaning she was unable to return home to Monaco. In a statement, it was explained that Charlene's medical team had instructed her not to travel.
Make sure you never miss a ROYAL story! Sign up to our newsletter to get all of our celebrity, royal and lifestyle news delivered directly to your inbox.