A 36-year-old Goulburn flight instructor and his 54-year-old Victorian passenger, named as Murray Valley businessman Andrew Goldman, died in the crash after the flight left Goulburn airport on Wednesday afternoon and was reported missing a few hours later.

NSW Police Detective Chief Inspector Brendan Bernie said police found the wreckage in a remote area near the Shoalhaven River just after midnight, but were unable to retrieve the bodies due to the difficult conditions and terrain.

It took emergency services several hours to navigate the rugged area overnight.

Chief Inspector Bernie said it was a tragic incident for the close-knit Goulburn community.

"We just hope the community rallies round and support the family and friends of these two pilots," he said.

"I'm sure both families are just devastated."

Specialist police will attend the scene on Thursday to undertake scientific investigations but Detective Chief Inspector Bernie said it was too early to speculate what caused the crash.

The flight which took off about 3pm Wednesday was due to be back some hours later, and police were notified of the missing aircraft when it hadn't returned about 6.45pm.

Chief Inspector Bernie believed the instructor had 670 hours of flight instruction experience and the trainee pilot had about 40 hours logged.

He appealed to anyone in the community who heard anything unusual in the area between 3.30pm to 6.45pm to contact police.