The win also made their Italian coach Carlo Ancelotti the first manager to capture titles in each of Europe’s top five leagues — England, Spain, Germany, Italy and France.
The Catalan club will play next season's games at an almost full-capacity Camp Nou but will relocate to the Olympic Stadium in Montjuic for the following campaign.
A sold-out Santiago Bernabeu stadium watched silently as a much-improved Barca under the command of new coach Xavi Hernandez dominated from the start.
Xavi probably could not have asked for much more in his first game managing a struggling Barca team who are sixth in the standings, eight points behind leaders Sevilla.
After the presentation Xavi talked about how discipline will be a major factor in his project as Barcelona manager.
The La Liga club received the green light on Friday to sign the 41-year-old after they paid the release clause in his contract with Qatari side Al Sadd.
The Argentine international received medical assistance on the pitch after he complained of chest pain during Saturday’s 1-1 draw with Alaves in La Liga and had to be taken to hospital.
The Barcelona strike complained about feeling dizzy during his side's 1-1 draw with Alaves on Saturday.
Koeman was sacked after Barca's 1-0 loss to Rayo Vallecano on Wednesday, their fourth defeat in six games in all competitions.
Local media reports suggest that former midfielder Xavi Hernandez, who is currently in charge of Al Sadd in Qatar, and Belgium coach Roberto Martinez are the frontrunners for the role.