The crash happened this morning at around 8.30am on the A259 at Hooe near Bexhill.
The man was taken to the Royal Sussex County Hospital in Brighton with serious injuries. He remains in a serious but stable condition, police said.
The road remained closed all morning and into the afternoon for crash investigation work.
The driver of the car was not injured.
Road closures were put in place in both directions between Little Common and Pevensey, and motorists are advised to find alternative routes.
Officers are appealing for witnesses or anyone with relevant information, such as dashcam footage, to report it to Sussex Police by emailing: collision.appeal@sussex.police.uk and quote Operation Murray.
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