Police were called to Rookwood Road shortly before 7pm, after multiple calls reporting a person walking on the road.
Before police arrived, a southbound B-double truck struck the pedestrian.
The driver immediately stopped and rendered assistance however, the woman died at the scene.
She is believed to be the woman who had been reported missing to police about 7am.
The driver, a 70-year-old man, was taken to hospital for mandatory testing.
Inquiries are continuing.
Anyone with information about this incident is urged to contact Crime Stoppers: 1800 333 000 or https://nsw.crimestoppers.com.au.
Missing woman struck and killed by truck
AN 85-year-old woman who died after being struck by a truck at Potts Hill last night is believed to have been reported missing from Guildford earlier in the morning.