The athlete, named as Moroccan boxer Hassan Saada, was detained earlier this morning, just hours before the Rio 2016 opening ceremony.
Police officers from the Recreio police station apprehended the athlete following the alleged attack on Wednesday.
It was claimed he tried to get one of the women to pose for a 'selfie' with him before asking if she was on social media. He then pushed her up against the wall and tried to kiss her, it was alleged.
He is also accused of sexually assaulting the second woman by groping her breasts. He then allegedly made sexually-graphic gestures towards the maid and offered her money to perform a sex act upon him.
The boxer will now no longer compete in the games.
Police chief Eduardo Ozório said the athlete had been detained after his officers had gathered evidence.