It happened around 3:30 Friday morning on North Dupont Highway near Boulden Boulevard.
Police say the 44-year-old male victim was standing in the southbound lanes when he was struck by a cargo van.
He was taken to Christiana Hospital Trauma Center in critical condition.
The driver - 52-year-old Lottie Schultz - was not injured.
Police have not released the victim's identity, pending family notification.