[14] He made his debut for the Spain national side on 23 April 1969, playing the second half of the 0–0 friendly draw with Mexico in Seville;[15] selected to the 1978 FIFA World Cup squad, he featured once in an eventual group-stage exit.

[19][20][5] When chain smoker Cruyff needed emergency heart surgery during the 1990–91 campaign, Rexach once again stepped up,[21] leading the side to their 11th league title – his first game in charge was on 27 February 1991, in a 6–0 home win against Las Palmas in the domestic cup.

[22] He remained in the position throughout the Dream Team era[23] and, after president Josep Lluís Nuñez sacked the Dutchman in May 1996, once again became head coach, a decision which allegedly cost him the friendship of Cruyff;[24][25] after new manager Bobby Robson replaced him with José Mourinho as his assistant he became a scout, going on to be responsible for discovering Lionel Messi.

[28] In the last matchday, following a 3–2 home defeat of Valencia and courtesy of a Rivaldo 87th-minute wonder goal, they managed to qualify for the Champions League;[29] this resulted in him being appointed coach by Joan Gaspart for the following season,[30] but after being ousted by Real Madrid in the semi-finals of the Champions League,[31] by Figueres in the Spanish Cup[32] and having lost the final of the Copa Catalunya to Balaguer,[33] he was fired and replaced by a returning Louis van Gaal, continuing to work with the club in directorial capacities.

[34] On 8 April 2010, Rexach announced his intention to run for Barcelona's presidency,[35] Nothing came of it eventually, but he was nonetheless chosen by new chairman Sandro Rosell as sporting advisor alongside Josep Maria Fusté and Migueli.