The 43-year-old was walking west on the A71 in Galston, East Ayrshire, when he was hit by a white Toyota Auris, which was also heading west.
Emergency services rushed to the scene near Barrwood Gate, but the man died.
Police Scotland are appealing for anyone who might have witnessed the incident, which took place at about 7.10pm on Saturday, to get in touch.
Constable Gordon Stewart of Irvine road policing unit said: “We are appealing for anyone who was in the area last night who may have seen the man prior to the incident, or the white Toyota Auris.
“We urge anyone with information or dashcam footage to come forward.”