Mr Rivlin, a former parliamentary speaker and Cabinet minister, defeated long-time legislator Meir Sheetrit, by 63 to 53 in a secret runoff ballot.
He will succeed Shimon Peres, 90, who ends his seven-year term in July.
The Israeli president occupies a largely ceremonial position and has no formal role in peace talks with the Palestinians.
Mr Rivlin, a member of the governing, right-wing Likud party, will become Israel’s 10th president.
He won in the second round of voting on Tuesday.
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