Rivlin, 74, beat lawmaker Meir Sheetrit of Hatnua party in a second-round runoff. Rivlin secured 63 to Sheetrit's 53 in the 120-member Knesset (the parliament).
The run up to the elections saw major aspirants face charges ranging from sexual misconduct to financial misappropriation leading to many analysts dubbing the elections "dirtiest" in Israel's history.
Peres' successor was chosen after two months of fierce political campaigning.
Rivlin will be sworn-in on July 24.
Five candidates were running for the president. The first round of voting eliminated former Supreme Court Judge Dalia Dorner, former Communications Minister and Knesset Speaker Dalia Itzik, and Nobel Prize-winning chemist Dan Shechtman.