It happened around 9:30 Sunday morning on the 2000 block of West Olney Avenue.
The area is known as Campus Boulevard for LaSalle University.
No word on what sparked the crash involving the ambulance and at least two other vehicles.
The elderly man was rushed to Albert Einstein Hospital but authorities say his injuries do not appear to be from the crash.
A 21-year-old female, 33-year-old male, 41-year-old female and a 79-year-old male were taken to area hospitals. All are listed in stable condition.
Traffic is shutdown in both directions along West Olney Avenue as an investigation continues.
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