The former Barca goalkeeper, 48, won 126 caps for Spain between 1985 and 1998, and replaces Txiki Begiristain who left with the outgoing president Joan Laporta earlier this week.
It has been a busy couple of days for new president Sandro Rosell and his board since taking the reigns on July 1 and they confirmed a number of other decisions on Friday.
Vice-president for sport Josep Maria Bartomeu said negotiations had started with Pep Guardiola on a new contract and that they would take up where the last board left off in their push for Arsenal's Spain midfielder Cesc Fabregas.
They denied a deal had been struck for Valencia's Spain winger Juan Mata and said they would stand by the deal reached with France striker Thierry Henry to rescind the last remaining year left on his contract, when he found a new team to play for.
The players loaned out last season would not be reincorporated into the squad, and clubs were being sought for them.
They include Belarus midfielder Aleksandr Hleb, Brazilian defender Henrique, Uruguay defender Martin Caceres and Brazilian forward Keirrison.
Rosell also said the position of honorary club president, created recently under Laporta and awarded to Johan Cruyff, was unconstitutional and would be revoked until club members could vote on the idea in a general assembly.
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