The singer-songwriter will perform an outdoor show at the foot of Shwedagon Pagoda in People's Square, Yangon on December 16.
Rolling Stone reports that the concert will also feature a number of local acts. Mraz is believed to be the first international artist to play an open-air concert in the country.
The 35-year-old said of the invitation: "I'm going there with an enormous amount of gratitude and respect, and I hope we can actually make a difference."
He added: "I hope it's also a testament to the songs. I've always wanted my songs to be about healing and self-empowerment, and if this is the way MTV is acknowledging that, then I am incredibly grateful."
Mraz became interested in anti-trafficking activism in 2008 after attending the Freedom Awards, an event recognising those who fight against human exploitation.
He said of the worldwide problem: "I thought this was something that was abolished when Abraham Lincoln signed the Emancipation Proclamation, but all it did is become hidden from our view.
"There was a recent estimate that there are about 27 million people enslaved on the planet, certainly due to hard economic times not just in the Western world but certainly in Third World countries. Humans as a commodity is a great way to run your business. So I signed on, lent my voice, lent my music to the cause."
The concert will be aired on the Burmese national television network, and will also air on MTV in countries around the world in 2013.
Jason Mraz is currently back in the UK charts, after his latest single 'I Won't Give Up' entered the top 40 last week at number 20.