The Brazilian forward sealed a €57 million switch to Camp Nou after making it clear he favoured a move to the Liga champions, but that did not prevent los Blancos from attempting to disrupt negotiations even when the contract was being signed, according to Rosell.
"When we reached an initial agreement with Neymar's father, the player had already passed a medical with Madrid, so we joked we would not bother with our own check-up," he told television station TV3.
"When we were signing the contract, Madrid were sending emails to Santos."
The Blaugrana president was also quashed the notion of their being any possibility of Real Madrid club captain Iker Casillas replacing the out-going Victor Valdes, despite the Spain No.1 having failed to regain his first-team place from Diego Lopez.
"Casillas will not sign because he is an icon of Real Madrid and I could not see him with the club badge on his chest, the same way I wouldn’t like to see Xavi in a Real jersey," said Rosell.
Finally, the 49-year-old revealed that tensions have dropped between La Liga's top two since Jose Mourinho's departure for Chelsea, but hinted he would miss the Portuguese's presence in Spain.
"Since then the tension has dropped, but his press conferences were entertaining," he added. "In the European Super Cup I was siding with Bayern Munich. Pep Guardiola is the best coach in history."
