Manchester United left-back Shaw was to the fore as England took an early lead, producing an excellent run and pass for Marcus Rashford to score in the 11th minute.
But with Spain 2-1 up, Shaw collided with visiting right-back Dani Carvajal and hit his head heavily on the turf before lying motionless in the 47th minute.
The 23-year-old received six minutes of treatment on the field before being carried off on a stretcher, wearing a neck brace and an oxygen mask.
Shaw, who revealed this week he came close to losing his leg after a serious break suffered while playing for United against PSV in 2015, was making his first international appearance for 18 months.
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