The approach came while Xavi was in charge of Qatari side Al Sadd.
The former Spain midfielder however opted to retrace his steps to Barcelona, where took charge as a replacement for Ronald Koeman in December.
Xavi helped steady the ship after taking over at the Camp Nou and was leading the La Liga table by two points when the bell for the World Cup break rang.
"It was an opportunity [that came] through the president of the CBF," Xavi told ESPN.
"They [came] to Qatar, and they talked to me, [and asked if] I could be part of Tite's staff.
"But I wanted to be a coach, not an assistant. My desire was to be a coach.
"It would be a tremendous opportunity - it was [a chance] to make history, to be the first European to work in the Brazilian national team.
"But, at that moment, it did not happen. I was clear that I wanted to be coach of Barcelona, which was my dream, and here I am."
Xavi has however not ruled out making the switch sometime in the future if the opportunity arose again.
"You never know. It would be a spectacular opportunity," he added.
"But my intention was to take over Barcelona. You never know about the future [though]. I'm working hard, and you can't rule anything out."
