The Holden Commodore was travelling at 205km/h in a 110km/h zone.
A man has allegedly been caught travelling at 205km/h, or 95km/h over the speed limit, on the Hume Highway.
NSW police said the officers from Holbrook Highway Patrol were on the Hume Highway near Little Billabong, west of the ACT, when they detected a Holden Commodore travelling at 205km/h in a 110km/h zone about 7am.
"Police stopped the vehicle and spoke to the driver, a 25-year-old man from South Australia," they said in a statement.
The driver's licence was suspended for six months, and he is expected to appear in court next month charged with driving at a dangerous speed and exceeding the speed limit by more than 45km/h.
