The horrific incident occurred near here yesterday when the 14-year-old girl, studying in the ninth standard, was returning home.
The accused, Balamurugan, who had fled the spot after committing the crime, was arrested today, the police said.
The accused had been pestering the girl to marry him and her parents had lodged a police complaint against him.
The police had also warned him.
Angered by the complaint, Balamurugan allegedly waylaid the girl, doused her with petrol and set her ablaze, the police said.