A learner driver was allegedly caught speeding at more than 100km/h above the legal limit during a police chase in the Hunter Valley.

The 26-year-old was driving on the New England Highway near Singleton about 9.30pm (AEDT) on Friday when officers signalled for the man to pull over.

Police say they gave chase after the man failed to stop, but the pursuit ended when the vehicle was allegedly clocked travelling at 184km/h - more than 100km/h above the legal limit of 80km/h for learner drivers.

The man was arrested a short time later when his Toyota Corolla was spotted in the grounds of a school, police said.

He was charged with a number of driving offences and was bailed to appear in Muswellbrook Local Court on December 7.