The accused, identified as Rohit Jayantilal Nandu, was a resident of Dahisar in north Mumbai, GRP officials said, adding they were trying to identify him for the last one and a half months.
According to the victim, a law student, on December 22 she was waiting for the train on platform number 3 of Khar station when an unidentified man accosted her and proposed to her, police said.
She declined and tried to ward him off, but he persisted. He fled when she called out for help, they said.
The CCTV footage showed him talking about a sweet shop in Malad area, so the police kept a vigil at the shop too.
After identifying him, Nandu was arrested from his house this afternoon and has been been booked under section 354 (molestation) of the IPC, GRP officials said.