parliament elected the even-keeled Labor veteran as its 11th president Wednesday, a vote that came as opposition lawmakers scrambled to forge a coalition to unseat .
Herzog, 60, beat former headmistress Miriam Peretz to replace President Reuven Rivlin, who was elected in 2014 to the largely ceremonial position decided by the parliament, or Knesset.
Wednesday's presidential vote came as Israeli politicians from across the spectrum were holding 11th-hour negotiations to cobble together a new administration aimed at ending Prime Minister Netanyahu's 12 straight years in office.
The Israeli presidency exerts little power, primarily meeting with party leaders after legislative elections and tasking candidates with forming governments. It is the country's prime minister who wields actual executive authority.
But the president does have the ability to grant pardons -- a potentially important function as Netanyahu faces trial for alleged fraud, bribery and breach of trust.
Herzog, who will assume his position on July 9, succeeded over Peretz, 67, a former headmistress who lost two children in Israel's wars and is known as "the mother of sons".
The scion of one of Israel's most prestigious families, Herzog was first elected to parliament in 2003, but was most recently leading the para-governmental Jewish Agency for Israel, an organisation focused on relations with Jewish immigrants and the diaspora.
His election on the day that could see Netanyahu's rivals make moves to take him down is fitting: in 2015 Herzog carried out a bid to oust the premier, presenting himself as a modest, diplomatic contrast to the bombastic "Bibi".
The son of Chaim Herzog -- Israel's sixth president and a former ambassador to the United Nations -- and nephew of the famed diplomat and statesman Abba Eban, the new president supports the two-state solution to the conflict with Palestinians.
During his 2015 campaign, he vowed to relaunch a peace process, even saying he was prepared to "remove" Israeli settlements if necessary.