Ms Caputova, who has almost no political experience, defeated high-profile diplomat Maros Sefcovic, nominated by the governing party, in a second round run-off vote on Saturday.
She framed the election as a struggle between good and evil.
The election follows the murder of an investigative journalist last year.
Jan Kuciak was looking into links between politicians and organised crime when he was shot alongside his fiancée in February 2
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She has won 58% of the vote, with Mr Sefcovic trailing on 42%.
Ms Caputova gained national prominence as a lawyer when she led a case against an illegal landfill lasting 14 years.