Rodri admitted it is his "dream" to play for Barcelona after he arrived in the city to complete his move from Premier League side Manchester City.
The World Cup and Ballon d’Or winner decided on the Catalan side despite talks with Real Madrid just weeks before which eventually fell through much to the shock of supporters.
Rodri, 30, has agreed a four-year deal with the Spanish champions who look likely to retain their title which would only frustrate Madrid even further.
Speaking on the rejection, Mourinho revealed that he did not want Rodri to be apart of this side after he expressed concern over the move which, for most players, is the dream switch.
“Real Madrid can not have players who think twice. You get the call and say: When do you want me there?
“Rodri is an extraordinary player, but Real Madrid is a different dimension. His doubts created doubts in me.
“I personally spoke to Rodri a couple of times. Real Madrid made him an important proposal.
“But then… Rodri had doubts. His doubts created doubts in me about signing him.”
The Spain captain, who was named the Player of the Tournament as La Roja won the World Cup this summer leaves City having won 12 major honours, including four Premier League titles, two FA Cups, three EFL Cups and the Champions League in 2022-23.
Madrid will be livid to see him sign for their bitter rivals and he should receive a cold reception when he visits the Bernabeu this season.