Barca, who were crowned champions when last season ended prematurely due to the coronavirus pandemic, dominated play from the start and took the lead in the 18th minute with a deflected strike from the edge of the area by Patricia Guijarro.
Madrid looked to have levelled when Sweden international Kosovare Asllani netted from close range after a spill from Barca goalkeeper Sandra Panos, but the goal was ruled out for a foul on the keeper amid angry protests from the home side.
Barca extended their lead early in the second half when Madrid defender Babett Peter diverted the ball into her own net after goalkeeper Misa Rodriguez had parried a cross from Barca's Norway international Caroline Graham Hansen.
Graham Hansen was a handful for Madrid's defence throughout and also set up the final two goals, a volley from former world player of the year Lieke Martens and a strike from Spain forward Alexia Putellas.
Real were playing their first match since completing the process to absorb local side CD Tacon in July, having competed in the top flight last season under Tacon's name and wearing their kit but training and playing at Real's training ground.
Their first official match at home to the club's eternal rivals was the subject of the cover of leading sports newspaper Marca on Sunday, although the occasion was subdued as coronavirus safety measures meant it was played without spectators.
But if Madrid could take one consolation from the day it was that at least the scoreline was not as humiliating as their last two matches against Barca when they were still called Tacon, losing 9-1 and 6-0
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