The vehicles crashed at the intersection of 76th Street and Woodside Avenue just after 7 a.m.
The force of the crash flipped the van onto the sidewalk.
75-year-old man Rashid Muhammad suffered a heart attack and was pronounced dead at the hospital.
The ambulance had a patient and was en route to the hospital. No criminality is suspected.
The drivers of the van, ambulance driver, and an EMT and patient inside the ambulance are all in stable condition at Elmhurst Hospital.