Stephen Shrimpton's bus overturned on the northbound M53 near junction five at Hooton, Cheshire, at around 8am on Friday. Jessica Baker also died in the accident.
The family of Mr Shrimpton, 40, said he is thought to have suffered a medical incident before the vehicle hit a reservation.
This has yet to be confirmed and a coroner's inquest will be held to establish exactly how the crash happened, once the police probe concludes.
A 14-year-old boy is understood to have suffered life-changing injuries, while a number of other pupils were also taken to hospital, where they were last night said to be "stable".
Eyewitnesses described how injured children climbed through windows of the bus to escape the wreckage.
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