The accident happened around 6:42 a.m. at the intersection of Route 129 and Lalor Street. That's where Trenton Fire Department Battalion Chief Todd Fell - driving a city-owned vehicle on his way to work - hit and killed the woman.
Todd reported the accident himself, police say.
As investigators processed the scene, the victim's black shoes could still be seen in the road.
"Right now it's all under investigation. The detectives are working on pulling video from the intersection to piece together what happened out there at the scene," said Sgt. Steven Varn of the Trenton Police Department.
Authorities have not yet released the name of the victim, who is believed to have visited a nearby Dunkin' Donuts just before she was killed. Police are questioning Chief Fell and attempting to locate witnesses to the fatal crash.
"Looking at the video briefly it appears that there were several people in the area when this occurred," said Sgt. Varn.
Route 129 and Lalor St. is a notorious intersection in town. It's been the scene of numerous accidents including a number of fatal crashes.
"So many people have died already," said Rosario Rodriguez, who is one of many area residents who are nervous crossing this busy intersection, which is right next to the light rail line.
The crossing guards who work during the day were not yet on duty when the accident occurred.
Police say it's too early to speculate on whether any charges will be filed. An autopsy for the victim is scheduled for Wednesday.