The eastbound M4 was closed for about 2 hours following the crash near Slough, Berkshire, at 8:15 am on Saturday.
Police said the man, aged in his 60s, died from his injuries.
A 24-year-old man from Swalwell, Gateshead, has been arrested on suspicion of causing death by dangerous driving and released while police inquiries continue.
Police have appealed for witnesses or dashcam footage of the incident, which involved a white Peugeot Boxer van and a silver Ford C-Max car between junctions six (Slough) and five (Langley).
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