Neymar has been linked to some of Europe's biggest clubs - including Real Madrid and Bayern Munich - in recent years, but declared his preference was to remain with Santos in his homeland until after the 2014 World Cup.
However, Santos announced on Friday evening that they had accepted two offers, allowing the 21-year-old to complete his move to Europe.
Barcelona followed in the early hours of Sunday morning with the announcement of Neymar's signing.
A club statement read: "FC Barcelona and Santos have agreed to terms for Neymar da Silva Santos Junior. The Brazilian forward will don the Blaugrana strip for the next five seasons.
The 21-year old is one of the most promising footballers on the planet."
Neymar also confirmed his decision, writing on Instagram: "I'm here with friends and family and they have helped me to write a few things here. I'm not going to hold out until Monday.
My family and friends already know my decision. On Monday I will sign a contract with Barcelona."
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