After an impressive 6-0 win over Portugal at Wembley on Friday, optimism in the England camp was high and they were looking to build on that display.
They beat Spain in February in the reverse fixture and knew progression to the Nations League semi-finals would potentially improve their 2027 Women's World Cup qualifying route.
But the hosts made it clear early on it would not be an easy task when Gonzalez was allowed to get on the end of a corner within three minutes, only to be denied by a superb Hampton save from close range.
England had been buoyed by the return of Bayern Munich midfielder Georgia Stanway – making her first start for her country this year after knee surgery in January - and there was a second successive start for key forward Lauren Hemp, who is also returning to full fitness.
Boss Wiegman gave another opportunity for Jess Park to stake a claim for a starting place at the Euros, selecting her ahead of Ella Toone, while Chelsea's Charles started at left-back.
But it was a tough evening for Charles, who was run ragged in the first half by Paralluelo and Pina's introduction in the second did little to relieve the pressure on her and the England backline.
With the home fans riled by a frustrating opening period, but later entertained by Pina's skilful impact, it added to the intensity and pressure faced by the Lionesses.
Aston Villa midfielder Missy Bo Kearns was thrown into the cauldron for her senior debut at half-time, replacing Stanway, and given a demonstration of the level needed if England are to defend their European title in Switzerland this summer.
It was also the first real test for keeper Hampton, newly confirmed as number one following Mary Earps' surprise international retirement last week.
The Lionesses were sloppy in possession and could barely get out of their own half as Spain's individual quality shone through in abundance.
La Roja are strong favourites for Euro 2025 and considered one of England's main rivals, but this result was not something to concern Wiegman too much - she was testing a few squad players and her side have shown previously they have the talent to trouble the world champions.
But the visiting supporters would have liked to have seen them back up their dominant display against Portugal and build momentum going into the Euros.
Wiegman names her 23-player squad for the tournament on Thursday and England have one match still to play before they travel to Switzerland, with Jamaica visitors to Leicester's King Power Stadium on 29 June.