The crash happened in the area of North Avenue and Vivian Terrace in Union Township around 5:15 a.m.
The 57-year-old victim, identified as John Monteverde of Whitestone, Queens, was apparently struck while the car was attempting to make a turn, and was pronounced dead at the scene.
The driver of vehicle was arrested and charged with DWI.
Union Police Lieutenant Robert Christie confirmed that the FDNY was assisting in the investigation.
Monterverde worked at Engine Company 159 in Dongan Hills.
FDNY Commisioner Salvatore Cassano released the following statement:
"The entire Department mourns the tragic loss of Firefighter John Monteverde, and we extend our deepest sympathies to his family and friends. John selflessly served the city for more than 31 years during which he was cited four times for his bravery at fires and for his life-saving medical work as a member of Engine Company 22 in Manhattan. He also devoted countless hours working tirelessly at the World Trade Center site in the rescue and recovery effort following the September 11 terrorist attacks, which took the lives of nine of his fellow firefighters at Engine 22 and Ladder 13. Our hearts and prayers are with his family and all those who knew and loved him."