Both recent winners of the Europa League, Tottenham Hotspur and Villarreal aim to take the first step towards Champions League glory in Tuesday's league phase opener in North London.
The Lilywhites conquered the second-tier tournament last season to return to the big time, while the visitors' fifth-placed La Liga finished sufficed for UCL football.
Set to reap the rewards of his predecessor's hard work, Thomas Frank leads Tottenham into Champions League battle on Tuesday after Ange Postecoglou masterminded Spurs' run to Europa League supremacy last season, their first major trophy in a long and torturous 17 years.
Seventeenth place ultimately took precedence over 17 years when it came to deciding Postecoglou's future, but barring one mishap at home to Bournemouth, the early signs under ex-Brentford boss Frank are highly promising for the hosts.
Tottenham reverted to type on Saturday with their third win and third clean sheet of the Premier League season, making extremely light work of London rivals West Ham United as Pape Sarr, Lucas Bergvall and Micky van de Ven all found the back of the net in a 3-0 victory.
Spurs already have one UEFA defeat next to their name this season, but they came out of their Super Cup loss to Paris Saint-Germain with a certain amount of credit, and the pre-game statistics make for pleasant reading thanks to last year's Europa League success.
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