The Houston Police Department said the incident happened just before 8 p.m. in the 9800 block of I-45 north, near West Road.
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Sgt. Dallas with HPD said witnesses reported seeing the man dart across the freeway, though it's unclear why.
Police said the man was hit by a white Nissan Sentra going northbound. He was pronounced dead at the scene.
HPD said the 34-year-old driver of the Nissan stayed at the scene. She was questioned and released, and it was determined she was not impaired.
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The pedestrian was 46 years old, but his identity is pending verification by the medical examiner's office.
An investigation into the incident is underway.