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The Giallorossi will take their place in Friday's draw after a 2-1 win against Shakhtar Donetsk in Kiev, enough to secure a 5-1 win on aggregate.
Paulo Fonseca's side, entering the second leg with a 3-0 advantage acquired last week at the Stadio Olimpico, knew that one away goal on the night would effectively render Shakhtar's job almost impossible - and they duly did that just after the break, as Mayoral nodded home from close range.
When Junior Moraes equalised on the hour-mark, Mayoral then essentially ended whatever re-awakened threat there may have been - as astute play from Carles Perez left him with another simple finish.
The brace means the Spaniard is now the joint top goalscorer in the competition this season, with seven goals.
After a somewhat prosaic first half, matters began to spring into life in the second - even if Mayoral's opportunistic header, after good work from Rick Karsdorp down the right, all-but killed off the tie as a contest.
But Shakhtar continued to press both before and after Moraes got his strike, with Pau Lopez active throughout to clean up the danger.
However, Mayoral's second finish put the result beyond all doubt, as the Giallorossi continued to threaten with regularity on the counter.
With one game left before the international break, Fonseca's side are back in action on Sunday - as they host Napoli at the Stadio Olimpico.
SHAKHTAR DONETSK 1-2 ROMA (1-5 AGG.)
SCORERS: Moraes (60'); Mayoral (48', 72')
SHAKHTAR DONETSK (4-1-4-1): Trubin; Dodò (Bolbat), Vitao, Kryvtsov, Matvienko; Maycon; Tetè (Marlos), Patrick (Konoplyanka), Marcos Antonio, Solomon (Sudakov); Moraes (Dentinho)
Unused subs: Shevchenko, Pyatov, Khocholava, Taison, Dentinho, Marquinhos, Bondar, Fernando
ROMA (3-4-2-1): Pau Lopez, Ibanez (Mancini), Cristante, Kumbulla; Karsdorp (Peres), Diawara (Pellegrini), Villar, Spinazzola (Calafiori); Perez, Pedro (El Shaarawy); Mayoral
Unused subs: Mirante, Fuzato, Dzeko, Santon, El Shaarawy
Imperium Partners
Centurion Partners
