Real beat Anadolu 90-85 in an absorbing clash with the lead changing hands time and again. A resilient Olympiakos drew level 1-1 with Barca after a 76-63 victory.
The two playoffs move to Istanbul and Athens respectively next week with Game Three scheduled for Tuesday and Game Four on Thursday.
Centre Felipe Reyes, who had a mainly quiet night, nailed a crucial three-pointer in a 15-3 Real run that forced a final twist in a rip-roaring contest that kept the Madrid fans on the edge of their seats throughout.
With both sides playing in fits and starts, Anadolu produced a 26-5 run in the first half to turn a 22-11 deficit into a healthy advantage and seemed poised to level the series after taking a 62-45 lead midway through the third quarter.
A hitherto misfiring Real replied with a barrage of three-pointers to nose ahead 68-67 before the Turkish outfit unleashed a flurry of their own to carve out an 82-75 lead in the closing stages.
Roared on by a fervent home crowd, Real delivered the killer blow in the last few minutes as Reyes, who finished on six points, buried an off-balance shot from behind the arc to give his side the lead for good.
Guard Sergio Llull led the winners with 18 points and 12 assists, former Portland Trail Blazers sharpshooter Rudy Fernandez netted 15 points and American KC Rivers added 14.
There was no such drama in Barcelona as Olympiakos, who won successive titles in 2012 and 2013, engineered an important 27-13 advantage in a dour and low-scoring first half.
Forward Georgios Printezis shone with 22 points and nine rebounds and playmaker Vassilis Spanoulis chipped in with 16 points against a subdued home side.
CSKA Moscow are 2-0 up against Panathinaikos and Fenerbahce Istanbul lead holders Maccabi Tel Aviv by the same score in the other two quarter-finals.
The playoff winners qualify for the May 15-17 Final Four in Madrid.
(Editing by Tony Jimenez)
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