Shaw injury overshadows Spain's comeback win
The 'Three Lions' went into the game looking to build on their impressive performances at the World Cup and they got off to the perfect start as they took the lead early on.
England won the ball back and set about countering, with Shaw marauding forward before sliding in the perfect low cross for Manchester United team-mate Marcus Rashford to slot past David de Gea first time.
However, their joy was shortlived as the visitors hit back just two minutes later through Saul. Dani Carvajal led a raid down the right before slipping in Rodrigo, whose cross dropped perfectly for the Atletico Madrid midfielder to sweep an effort beyond the outstretched hand of Jordan Pickford at the near post.
That goal got Spain's tails up as they enjoyed the bulk of the possession for the rest of the half.
The hosts felt they should have had a penalty when Harry Kane received a nudge in the back from Carvajal when trying to meet Harry Maguire's knockdown and with just over 30 minutes gone Spain completed their comeback.
England switched off when looking to defend a free-kick from out on the left, allowing Rodrigo to stroll in and prod Thiago's delivery into the corner at the near post.
Rashford almost restored parity a couple of minutes later, only for club team-mate David de Gea to produce a stunning one-handed stop to keep out his header from a left-wing corner.
With that the visitors went in ahead at the break, with the game's main talking point coming just minutes after the restart.
Shaw and Carvajal collided in the air out on the England left, with the Manchester United man coming off worse. The 23-year-old appeared to take a shoulder to the face before his head crashed off the turf on landing.
The left-back was quickly attended to by medical staff from both sides, with United and England now facing an anxious wait to discover how long he will be out for.
England struggled to settle for a period after Shaw was stretchered off, with Thiago fizzing a volley narrowly over Pickford's crossbar.
The hosts came more into the game late on, though, as they looked to claim something from the game, Rashford doing brilliantly to create a yard of space for himself on the edge of the box, only to fire straight at De Gea.
There were nine minutes added on at the end of the game due to Shaw's injury and it was during that time that England thought that had drawn level.
De Gea made a mess of collecting a high ball, eventually contriving to drop the ball at the feet of substitute Danny Welbeck, who duly tapped home the loose ball. However, England's celebrations were cut short as the referee awarded a foul against the Arsenal man, meaning England's late charge came to nothing.
The defeated ended a run of 14 straight wins in competitive games at Wembley for England, who must now prepare to take on Switzerland in a friendly next week. Spain, meanwhile, turn their attentions to their next UEFA Nations League clash with Croatia.