Liverpool suffered an injury time sucker punch in Villarreal after a defensive display in the 90 minutes of normal time.
Klopp, as has become familiar for European games, left Sturridge on the bench - this time joined by Benteke who marked a return from injury.
Liverpool as a result were compact although they lacked the firepower to break down a defensive Villarreal. The Spanish side have one of the meanest defences in Europe.
The reds did have their chances - Firmino hit the post and Lallana was denied a one on one with the keeper when he was wrongly ruled offside after a perfectly timed second half run.
In the opening minutes Joe Allen could have given Liverpool a dream start but fired straight at the keeper.
Sturridge spent the half time break training on the pitch but he wasn't brought on in the second half, and Benteke was late on. But it was Villarreal who got the important late goal that gives them a big advantage ahead of next weeks second leg at Anfield.
Liverpool had lost Coutinho at half time - removed because he wasn't feeling well - and Jordon Ibe was sent on to replace him.
This didn't help matters.
For Villarreal their veteran midfielder Bruno was at the heart of all their good moves - unlocking Soldado who failed to show the Premier League what they were missing. On the night his shots were generally high and wide.
Alberto Moreno made one counter from an opposition corner - running the length of the pitch being chased down but his shot went wide. Had it gone in it would definitely have been 'unbelievable Jeff'.
Mignolet was called on to produce an impressive save late on but he couldn't keep out Villarreal's winner.