Banco Santander's board of directors unanimously agreed to appoint Botin's eldest daughter Ana to replace him as chair, the company said in a statement. Aged 53, Ana Botin was CEO of Santander UK in London.
Born into a family of bankers, Botin was known for his hands-on leadership. He turned Banco Santander, previously run by his father, into Spain's biggest and then into the eurozone's largest by market capitalisation through a prolonged and aggressive series of acquisitions. He also transformed it into a major bank in Latin America.
Spanish Prime Minister Mariano Rajoy said Botin seemed fine and in good health when the two had a meeting last week.
His death is "a surprise and at the same time a big blow. He was a great ambassador for the Spanish brand," Rajoy told reporters in the halls of Parliament.
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A bank spokeswoman said he died last night after suffering a heart attack at his home. She spoke on condition of anonymity because of company rules preventing her from being named.
One of his daughters was married to famed Spanish golfer Severiano Ballesteros, who died in 2011. And through Santander, Botin was a sponsor of Formula 1 racing, in particular Spanish driver Fernando Alonso.
Under his leadership, the bank boosted its name recognition and influence across Spain by financing university programs, scholarships and social and cultural events.