The Spanish giants have contested the final in each of the past two years, with Barcelona triumphing in 2012 and Real claiming glory 12 months ago.
They appear on course for a third successive meeting after victories at the weekend earned them both a 2-0 lead in the best-of-five series.
Barcelona, who have appeared in the final in each of the past seven seasons, edged past Valencia 60-59 thanks to Ante Tomic’s basket two seconds from time.
Justin Doellman and Sam van Rossom led the way for Valencia with 16 and 13 points respectively, with Marcelo Huertas (11) top-scoring for the visitors.
Barca trailed by one entering the final seconds, but Tomic picked up a rebound under the net and sunk the basket to take his tally to nine points and put his side in control of the series.
Real came through a similarly tight encounter, prevailing 89-87 at home to Unicaja.
Madrid had finished top of the table at the end of the regular season, while Unicaja had ended fourth, but it was the visitors who forged ahead, 26-22 at the end of the first quarter.
A strong third quarter from the hosts saw them move 70-66 in front and although Unicaja got the better of the fourth 21-19, it was not enough to overturn the deficit as Madrid moved 2-0 up in the series.
Rudy Fernandez (18 points) was the standout player for Madrid, while Jayson Granger and Fran Vasquez both matched that tally for Unicaja in what proved to be an ultimately fruitless endeavour.
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