The Blaugrana had long been linked with a move for the left-back, and are now one step closer to completing the deal after negotiating a €14 million fee.
Alba will undergo a medical next week, and sign a five-year deal upon successful completion of his physical examination.
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"Barcelona announce that today an agreement with Valencia has been reached for the transfer of Jordi Alba, pending a medical examination. The player will undergo in Barcelona next week," an official statement reads.
"The cost of the transfer will be €14m and the player will sign a contract for the next five seasons."
Alba, 23, is a product of the Barcelona youth academy, but failed to break into the first team at Camp Nou and left the club in 2005.
He will now return to his boyhood outfit after spells with Cornella, Gimnastic and Valencia.