Manchester City have rejected an opening offer worth around £38.5m from Barcelona for Rodri, with the Premier League club understood to be holding out for a fee in excess of £60m for their Spain international.
The 30-year-old enters the final year of his contract at the Etihad Stadium and is yet to sign an extension, with his future the subject of intense speculation throughout the summer.
Real Madrid had appeared to be the frontrunner to land him, but Barcelona have overtaken their rivals after sources indicated the club had the player's blessing to open negotiations with City, an offer that duly followed on Friday. Talks between City and Real Madrid over a move are now understood to have ended.
Rodri's representative has since confirmed the decision publicly.
"Out of respect for Real Madrid, who have acted very professionally, Rodri informed them he has decided to join Barça," agent Pablo Barquero told Spanish radio station El Larguero, ending weeks of uncertainty over which of the two Spanish giants would land the midfielder.
Barquero's confirmation follows a summer in which Real Madrid had appeared to hold the advantage, with the Bernabéu club reportedly in agreement with the player over personal terms on a four-year contract before Barcelona's late intervention changed the picture.
Barcelona sources had initially cautioned that no deal was guaranteed, but the situation has since developed quickly: the club confirmed on Friday it was in ongoing discussions with Rodri's representatives before following up with its opening bid the same day.
Manchester City, now managed by Enzo Maresca following Pep Guardiola's departure at the end of last season, are not thought to be actively pushing for a sale but remain open to letting Rodri leave if their valuation is met.
The midfielder joined City from Atlético Madrid in 2019 and has since become one of the club's most important players, winning multiple Premier League titles and the Champions League among a host of honours, as well as the 2024 Ballon d'Or.
With personal terms already in place between player and Barcelona, the deal now hinges on the two clubs closing the gap over a transfer fee before the Spanish club can complete what would be one of the summer's biggest moves.