It happened at 2:20 a.m. Thursday in the westbound lanes of Route 2 (Capital Trail) near Darwin Drive.
State police say the victim, a 49-year-old woman, was wearing dark clothing, not carrying a flashlight and not walking in a cross walk when she stepped into the path of an oncoming 2007 Volkswagen Jetta.
She was struck and thrown to the side of the road. Medics pronounced her dead at the scene.
Investigators say alcohol use by the victim may have played a role.
The 33-year-old driver of the striking vehicle stopped nearby and was not injured.
Police say no charges are expected to be filed.
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