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Montezemolo already sits on Unicredit's board as a representative of Abu Dhabi investment vehicle Aabar, which is the bank's single biggest shareholder with a 6.5 percent stake.
UniCredit's vice chairman post was previously held by the head of Aabar, Khadem Al Qubaisi, who stepped down earlier this month.
The bank's governance and nominations committee will propose Montezemolo's appointment to the board on Oct.18, UniCredit said. Mohamed Ali Al Fahim, head of the finance division at Abu Dhabi's investment company IPIC, will replace Al Qubaisi as a board member.