Czech stars Jan Vesely, who joined Barcelona from Fenerbahce in the summer, and Tomas Satoransky were on fine form early on, scoring their fair share points from inside the three-point line to give the hosts a 10-point lead after the second quarter.
Their advantage grew by a further point in the third quarter with Sertac Sanli getting in on the action. He would finish the game with 14 points and three rebounds, including two from distance.
But Real Madrid - potentially spurred on by the rivalry - were not finished yet and fought well to reduce the arrears in the final period.
Argentine Gabriel Deck, who top scored in the game with 21 points, helped pull the defecit back with an impressive record of seven of eight free throws scored. Despite scoring nine of the final 10 plays of the game, Real Madrid ran out of time, giving Barcelona the bragging rights in El Clasico.
Check out everything from the first El Clasico of the weekend with Flashscore.
Red Star Belgrade - Panathinaikos 75-77
Panathinaikos got their first win of their EuroLeague campaign with a closely fought win over Red Star. The hosts got off to a fast start, leading by six points after the first quarter. The Greek outfit fired back soon after, putting up 24 points in the second quarter to lead at the half by four.
Ben Bentil was the player with the most points in this contest, scoring 18 points with six rebounds. However Panathinaikos' Lithuanian pair of Marius Grigonis and Arturas Gudaitis kept pace with the Ghanaian, scoring 17 and 12 points in the game respectively.
After the third quarter, the gap between the two sides tightened to just a point, but the visitors rallied as time ran down to pick up the victory.
Check out all the stats from the game with Flashscore.
Monaco - Anadolu Efes 95-92 AOT
Last year's champions Anadolu Efes were defeated for the first time this season after an overtime loss to a Monaco team that continued their strong start to the EuroLeague season.
In a topsy-turvy encounter, the Monagasques fell behind early but rallied in the second quarter - Mike James once again showing hot hands, top scoring for the home side on a night of drama.
For Anadolu, they relied on American Will Clyburn and Serbian guard Vasilije Micic for their points. Both delivered, scoring 27 and 20 apiece, but their teammates could not back them up as Monaco's players shared the points around more evenly.
The hosts took the game to overtime with the final points of the fourth, and took the momentum with them to secure a morale boosting victory against Anadolu.
Find out all of the stats from the encounter with Flashscore.
Virtus Bologna - Bayern Munich 66-63
Bayern slipped to their second defeat of the league with a 66-63 defet at Virtus Bologna. After a humbling loss last week, the German side struggled to get going and found themselves eight points down after the first quarter, only to hit back and reduce the arrears to just two at the half.
Nick Weiler-Babb was on form for the visitors, scoring 16 points with five rebounds and four assists, however his performance was not enough to get the win as Bologna held on to win by three.
