Valencia's substitutes made the difference with two late goals to earn a 2-0 victory in the away leg of their last-32 Europa League tie with Dynamo Kiev on Thursday night.
Eduardo Vargas and Sofiane Feghouli, both second-half replacements, scored in the 80th and 90th minutes respectively to put the Spanish side in charge of the tie.
The match was played in Nicosia, Cyprus, because of the ongoing violent clashes in the Ukrainian capital and it was the designated visitors who adapted better, squandering chances to take the lead before finally making the breakthrough.
Fiorentina also established a commanding first-leg lead thanks to a 3-1 success at Esbjerg.
Alessandro Matri put the Serie A side ahead after only eight minutes and, even though Martin Pusic levelled two minutes later, Josip Ilicic made it 2-1 to the Italians after 15 minutes.
Alberto Aquilani added a third from the penalty spot before the break to leave La Viola on the verge of the last 16.
Another Italian side Juventus won their home leg against Trabzonspor 2-0.
Dani Osvaldo opened the scoring with his first goal for the club after 15 minutes and Paul Pogba doubled their advantage deep into stoppage time.
Benfica were 1-0 winners at PAOK Salonika thanks to Rodrigo Lima's second-half strike, while AZ Alkmaar won by the same scoreline at Slovan Liberec, Nick Viergever with an 89th-minute winner.
Elsewhere, the matches between Chornomorets and Lyon and Anzhi Makhachkala and Genk finished goalless, with Russians Anzhi ending their match with 10 men following the 89th-minute red card for Ilya Maksimov.