AEK beat 1967 champions Celtic 2-1 in a fervent atmosphere in Athens for a 3-2 aggregate win over the Scottish side while PAOK held out for a 0-0 draw at Spartak Moscow after edging the Russian outfit 3-2 in the first leg.
Benfica, champions in 1961 and 1962, earned a 2-1 overall win over Fenerbahce after a 1-1 draw in Istanbul and four-time winners Ajax Amsterdam cruised to a 5-2 aggregate defeat of Standard Liege.
Red Star Belgrade, the 1991 champions, overpowered Spartak Trnava 2-1 away after extra time for a 3-2 overall victory over the Slovakian side who missed a penalty in the dying seconds.
Rodrigo Galo swept in a low cross from the right and Marko Livaja headed in the second for AEK before Scott Sinclair pulled one back for Celtic to set up a dramatic finish.
The outcome was a bitter blow for Celtic manager Brendan Rodgers while AEK will be relishing a two-legged clash with Hungarians Vidi FC for a berth in the lucrative group stage of the competition.
PAOK, who fought back from 2-0 down in the first leg against Spartak, were helped in the return leg when the home side's striker Luiz Adriano was sent off in the 33rd minute for a foul on Jose Angel Crespo.
PAOK will face Benfica for a group stage berth, with the Portuguese giants tightening their grip when midfielder Gedson Fernandez fired them ahead in Istanbul before Alper Potuk equalised on the night.
Quickfire first-half goals by striker Klaas Jan Huntelaar and defender Matthijs de Ligt put Ajax firmly in control against Standard and David Neres added the icing on the cake with a third shortly after the break.
The Dutch side's reward is an intriguing clash with Dynamo Kiev, who eliminated Slavia Prague 3-1 on aggregate after goals by Benjamin Verbic and Artem Besedin fired the Ukrainian side to a 2-0 home win over the Czechs.
Red Star fell behind to an early Marek Bakos header in Trnava but replied instantly through El Fardou Ben Nabouhane before Serbia winger Nemanja Radonjic sealed the contest with a superb finish into the top corner in the 98th minute.
Red Star, who have never qualified for the Champions League group stage, will meet Salzburg after the Austrian team strolled into the play-offs with a 4-0 defeat of Macedonians Shkendija.
Belarus champions BATE Borisov face PSV Eindhoven after a 2-1 aggregate win over Azerbaijan's Qarabag while Dinamo Zagreb eased to a 3-0 overall rout of Kazakhs Astana for a clash with Young Boys Berne.
(Writing by Zoran Milosavljevic; Editing by Pritha Sarkar)
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