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The last three matches between the sides have finished level, with the most recent two goalless, and it would be a surprise if it proved to be a one-sided affair this time.
Portugal won the inaugural Nations League back in 2019 while Spain were beaten in the final by France two years ago. The two are joined in their group by Switzerland and the Czech Republic.
With home matches to come against those two sides in the next week, Cristiano Ronaldo and Portugal know that they will put themselves in a great position to take control of the group should they return from Spain with all three points.
Where to watch Spain vs Portugal
TV channel: Spain vs Portugal will be shown live on Premier Sports 2 - it costs £9.99 for a monthly subscription in the UK.
Live stream:Premier Sports subscribers will also be able to watch the game online via the Premier Player on mobile and tablet devices.
Live blog: You can follow all the action with updates from Standard Sport’s live match blog this evening.