Los Blancos added a couple of goals to their tally at the Bernabeu in Wednesday evening's second leg for a 2-0 home win, seeing them close in on their opponents' tally of 12 titles.
Marco Asensio and Karim Benzema netted the only goals of the night, ensuring that Madrid have kicked off their 2017-18 campaign in style by lifting both the Supercopa and UEFA Super Cup in the past week.
Madrid, sitting on that two-goal lead from the first leg at Camp Nou, were unwilling to simply protect their advantage and instead went all out for another right from the off.
They were rewarded for their positivity, too, as Asensio added another gem to his growing collection by picking out the top corner of Marc-Andre ter Stegen's net with a fine strike from 30 yards out.
Barca slowly started to grow into the game a little but, a Luis Suarez volley over the bar aside, they did little with their possession and were soon made to pay.
The home side had far more about them in attack, utilising their pace and power and coming within inches of adding a second when Lucas Vazquez - given the nod over Isco and Gareth Bale from the off - picked out the post with his curled attempt.
Toni Kroos also failed to find a way through when picked out in a good position, but it would matter little as Benzema made sure of the victory for his side 39 minutes in thanks to a well-taken goal.
The Frenchman required one touch to set the ball and another to drill it into the bottom corner, giving Los Blancos plenty of breathing space with a quarter of the two-legged tie still to play.
Visiting boss Ernesto Valverde went with three at the back, but was forced into a reshuffle early in the second half when Gerard Pique left the field with a slight knock to be replaced by summer signing Nelson Semedo.
Barca were desperately seeking a goal to potentially revive the tie, but they knew it was not going to be their night when Lionel Messi drifted away from his man and lofted the ball over Keylor Navas, only for the crossbar to come to the hosts' rescue.
Benzema and Suarez both came close for their respective sides as the hour mark approached, forcing saves out of the opposition keepers from inside the box.
Suarez was proving to be Barcelona's best hope of netting a consolation, heading the ball against the post after Messi's initial shot was parried by Navas, having also set up a chance for Roberto which the wing-back failed to take.
There was to be no joy for Valverde, however, as he became just the third Barcelona manager to lose his first two competitive games in charge of the club.