Porto is the runaway leader of the Portuguese league and breezed through its group by winning five and drawing one of its six matches.
Sevilla, which won Europe's second-tier competition in 2006 and '07 when it was called the UEFA Cup, edged into the last 32 courtesy of a draw against Borussia Dortmund in its final group game and is in disarray in the Spanish league, losing its last four matches.
Whichever team advances will play either 2005 winner CSKA Moscow or PAOK Thessaloniki in the last 16.
In another match between two former winners, Anderlecht will meet Dutch giant Ajax, which dropped into the competition after finishing third in its Champions League group.
Villarreal, which is third in the Spanish league, will take on Napoli, the only Italian team left in the competition, and five-time European champion Liverpool was drawn against Sparta Prague in the last 32.
Greek side Aris' prize for helping eliminate defending champion Atletico Madrid in the group stage is a match against big-spending English club Manchester City.
PSV Eindhoven, which won the European Cup in 1988, was paired with French side Lille.
Russian side Zenit St. Petersburg was only team to win all six of its group matches and the 2008 champion will next face Young Boys of Switzerland.
The first of the two-legged last-32 matches are scheduled for Feb. 17, with the return games on Feb. 24.
The last-16 matches will be played on March 10 and 17.
(Matches to be played February 17 and 24)
Napoli (ITA) v Villarreal (ESP)
Rangers (SCO) v Sporting Lisbon (POR)
Sparta Prague (CZE) v Liverpool (ENG)
Anderlecht (BEL) v Ajax (NED)
Lech Poznan (POL) v Sporting Braga (POR)
Besiktas (TUR) v Dynamo Kiev (RUS)
FC Basel (SUI) v Spartak Moscow (RUS)
Young Boys Berne (SUI) v Zenit St Petersburg (RUS)
Aris Thessaloniki (GRE) v Manchester City (ENG)
PAOK (GRE) v CSKA Moscow (RUS)
Sevilla (ESP) v Porto (POR)
Rubin Kazan (RUS) v FC Twente (NED)
Lille (FRA) v PSV Eindhoven (NED)
Benfica (POR) v Stuttgart (GER)
BATE Borisov (BLR) v Paris St Germain (FRA)
Metalist Kharkov (UKR) v Bayer Leverkusen (GER)