The outspoken Portuguese as ever ruffled feathers off the pitch with his controversial comments, criticising referees, kick-off times and accusing Barcelona of favouritism, however, on the pitch Real were again second best to their arch rivals.
Mourinho landed his first trophy as Madrid boss with the Kings Cup, all the sweeter given that the final win was over Barcelona.
But the more prestigious pieces of silverware escaped Real as Barcelona won a third successive league crown and ousted their foes in the semi-finals of the Champions League.
Real and their expensive collection of 'Galacticos' were widely criticised for their negative tactics against Barca, while Mourinho had to endure a 5-0 mauling in his first Clasico and the end of his nine-year unbeaten home league run.
After two years without a trophy, the Kings Cup was welcome for Madrid fans but it could not compensate for painful losses to Barca, as the two teams met four times in 18 days, in Europe and a failure to keep pace in the league.
Mourinho came with a proven track record for success after winning league titles with Porto, Chelsea and Inter Milan along with two Champions League titles, with the most recent being in Madrid when his Inter side lifted the coveted trophy.
He splashed out money on Ricardo Carvalho, Sami Khedira, Angel di Maria and Mesut Ozil and immediately talked of an unprecedented 'Grand Slam' of winning league titles in Italy, England and Spain.
Real had not won the Champions League since 2002 and Mourinho also vowed to try and bring a 10th European Cup and in the process become the first coach to win the trophy with three different clubs, having achieved it with Porto and Inter Milan.
The Portuguese had a forgettable debut as his Real Madrid started with a drab 0-0 league draw at Real Mallorca, but things improved and 32 points from a possible 36 made Mourinho the most successful managerial debutant in La Liga.
On the pitch Real were building a reputation as a lethal counter attacking team, using the fleet-footed wingers Cristiano Ronaldo and di Maria to cut through teams.
Heading into the first 'El Clasico' at Nou Camp in late November, Real were a point above Barcelona and looking to go four points clear.
It was a first taste of the fixture for Mourinho and it turned into a nightmare as Barcelona thrashed Real 5-0 - a fifth successive defeat for the 'meringues'.
"They played well and we played very poorly," said Mourinho. "It is a defeat - not a humiliation."
The loss was Mourinho's heaviest of his glittering managerial career as Real paid the price for coming out to attack and it had an impact on Mourinho's future tactics for the four subsequent Clasicos.
In the league Madrid were chasing, as they had done for the previous two seasons, trailing Barcelona by two points and only the goals of Cristiano Ronaldo, who has 36 in the league so far, kept them in touch.
In 2011 Real's erratic away form proved their undoing as a 1-0 loss at Osasuna and draws against Almeria and Deportivo La Coruna allowed Barca to go five clear at the summit.
In the league match before the second league Clasico, Real fell to a surprise 1-0 home loss to unfashionable Sporting Gijon as Mourinho's 150 game unbeaten league home record, stretching back nine years to February 2002, came to an end.
Barcelona were eight points clear and a 1-1 draw at the Santiago Bernabeu in the second league Clasico ended Madrid's comeback hopes.
Real had something to cheer four days later when a Ronaldo goal in extra time downed Barcelona 1-0 in the Kings Cup final.
It lifted spirits ahead of the semi-final duels but despite home advantage in the first leg Mourinho instructed his team to play deep and a brace from Lionel Messi punished 10-man Real who had Pepe sent off on the hour mark.
Mourinho ranted after the match about Pepe's red card, criticised referees and claimed Barcelona received special treatment.
"I don't know if it is the Unicef sponsorship or if it is because they are nice guys. I don't understand," said Mourinho. "They (Barcelona) have power and we have no chance."
The return leg of the Champions League semi saw Barcelona draw 1-1 and progress 3-1 on aggregate to the Wembley final, while Mourinho and his players continued their conspiracy claims, with a disallowed Gonzalo Higuain goal their latest complaint.
As expected Barcelona clinched the league title and for Madrid the season was over with their Kings Cup win little consolation.