The accident occurred around 6:20 p.m. Monday when Michale C. Brailey of Red Hook, who was driving his white 2013 Ford F-150 north on Route 9W when his pickup truck left the roadway and struck a bicyclist, the department said.
The bicyclist, Justin Boyd, also age 33, of Port Ewen in Ulster County, died at the scene, the Sheriff's Office said.
Sheriff's deputies, along with help from the state police Collision Reconstruction Unit are investigating the incident.
Deputies were assisted at the scene by the Port Ewen Fire Department and the Town of Esopus Volunteer Ambulance Squad.
Jason Brodbeck contributed to this report.
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