Sweden romped to a 6-1 win over Scandinavian rivals Denmark to progress to the final four, along with already-qualified France and Germany.
World champions Spain won Group A3 by five points from Euro 2022 winners England, who could have progressed themselves with a victory at the RCDE Stadium on the outskirts of Barcelona.
Alessia Russo stroked Sarina Wiegman’s side ahead after 22 minutes, but Pina’s brace off the bench in the second half booked Spain’s ticket to the final four in October.
Spain and England will be the favourites to lift the Euros trophy this summer in Switzerland and after a narrow defeat at Wembley in February, Montse Tome’s side flexed their muscles by outclassing the Lionesses.
Pina did the damage with a cool first finish and then a blast from the edge of the box for her second.
“I received the ball (for the second) and I didn’t even think about it, I hit it with my soul,” said Pina, who often shines off the bench for her club too.
“I always try to do my best, and I am ready, I’m happy to be able to help,” she added.
Featuring seven Barcelona players, who finished as Champions League final runners-up last week, and one winner in Arsenal’s Mariona Caldentey, Spain started the stronger.
They almost took the lead after three minutes but Hannah Hampton made a superb reflex save to deny Esther Gonzalez from close range.
The Chelsea goalkeeper was under the spotlight after Mary Earps’ shock decision to retire from international football ahead of the Euros this summer and swiftly offered evidence of why she is England’s number one.
Despite the hosts’ dominance they could not find a way in front and England capitalised.
Niamh Charles got away with a slight foul on Salma Paralluelo inside her own half which enabled England to spring forward.
Former Barcelona midfielder Keira Walsh guided a superb ball through for Russo to chase and the Arsenal forward stroked home clinically.
Spain were left outraged when left-back Charles then blatantly handled the ball in her area without punishment.
Spain, who beat England in the 2023 World Cup final, found a way back through substitute Pina, who netted two minutes after coming on.
Pina flashed a quick shot across Hampton to equalise, and the 23-year-old grabbed another 10 minutes later.
She bagged her second from the edge of the box, with a shot which crashed in off the post past the helpless Hampton.
England never seemed capable of wrestling the momentum away from a Spain side that began to cruise, starving the visitors of the ball.
They were run ragged and beyond missing out on the Nations League will be left with some concerns ahead of their European Championship defence this summer.
“It was a very intense game,” Wiegman said. “They are very tight on the ball, I thought we did well. In the second half they were pressing a bit higher and we struggled to get out of the press and keep the ball.”
England midfielder Fran Kirby announced her retirement from international duty after the game, having been told earlier in the week she would not be part of the Euros squad.
“I’m really proud of her and grateful to work with her over the years,” Wiegman told reporters. “She’s been an inspiration for a lot of people and an incredible example.”
With Earps and Kirby retired and question marks over Millie Bright’s availability after she stepped away from the camp because of burn-out, England could lack some experience in their Euros squad.
Sweden clinched Group A4 victory with a thumping triumph against sorry Denmark.
Stina Blackstenius followed up her Champions League-winning goal with a hat-trick at the Strawberry Arena in Solna to inspire her team to victory.
France, who were runaway winners of Group A2, beat Iceland in their final match with goals from Sandy Baltimore and Grace Geyoro.
Group A1 winners Germany thrashed Austria 6-0, while Scotland earned their first point with a surprise 1-1 draw against the Netherlands. (AFP)