Reds travelling to Valencia on a Ryanair flight not from London Stansted will have to make other plans to get to the Villareal game after the airline cancelled all flights leaving after November 4.
Passengers travelling on Ryanair from Liverpool Airport or East Midlands after that date will get a full refund, a Ryanair spokesman has said.
It follows a dispute between the company and Valencia's local government officials over how the region should be promoted to tourists.
A Ryanair spokesman said: "Ryanair will continue to operate a limited service to Valencia on a London Stansted-based aircraft.
"Passengers who were due to travel on affected flights to and from London Stansted may be able to transfer to one of our London-based services or can receive a full refund.
"Passengers due to travel on all other cancelled Valencia-based services, will receive a full refund from Ryanair."
Other flights from the UK to Valencia are touching £150 for a return on the week of the match, which takes place on November 25.
Alternative routes to Villareal are from: Manchester, Liverpool, Leeds and Birmingham to Alicante, Reus, Barcelona International and Girona.
See the in-depth travel guide below for the best flights.
All passengers should receive an email giving details of how to get their money back.
If you need to contact Ryanair, you can only do so by mail or fax. Its refunds address is: For Ryanair Refunds Dept, PO Box 11451, Swords, Co Dublin, Ireland. Fax is: +353 1 8121676.