Kidjo grew up in Benin, but left for Paris in 1983, citing oppression from the country's then-communist government.
"From the moment the communist regime arrived in Benin, I became aware that the freedom we enjoy can be snatched away in a second," she told the BBC in 2023.
The Walk of Fame ceremony was also filled with singing and dancing in celebration of Kidjo's career, which has included collaborations with big names such as Burna Boy, John Legend, Bono and Alicia Keys.
Her latest album, HOPE!!, was released earlier this year with tracks produced by Pharrell Williams, and collaborations with Ayra Starr, Quavo, Nile Rogers and Diane Warren.
She has released 18 albums in total and has been nominated for 17 Grammy awards, which she has won five times.
The songstress also won the 2023 Polar Music Prize, and two years earlier was named as one of Time's 100 Most Influential People.
"She is without a doubt the hardest working woman in showbusiness," Dafoe said at the ceremony.
"The first time I saw Angélique perform live, I thought her music, her dancing, her commitment were incredible."
The Spider-Man star likened her energy to that of soul singer James Brown, who he called the "hardest working man in showbusiness".
"She's not only an incredible performer - she doesn't pop on the mic like I do - songwriter and musician, but also an incredibly kind and giving person and a real deal activist."
Kidjo is a Unicef and Oxfam goodwill ambassador, and is the co-founder of the Batonga Foundation, which helps vulnerable young girls and women in Benin.
At the Los Angeles gathering she was also praised by Harvey Mason Jr, the CEO of Recording Academy - the organisation that also oversees the Grammy awards.
"She's connected cultures, she's crossed borders, she's reminded audiences everywhere that while we may come from different backgrounds, her music unites in a way that few other things can," he said.
Kidjo joins Charlize Theron, a white South African actress, in representing Africa on the Walk of Fame, which comprises more than 2,800 stars.