Abstract Native oxide removal on GaAs wafers under conventional thermal desorption causes severe surface degradation. Recently a new method of Ga assisted oxide removal has reported improved initial surface conditions. A precise dosing of Ga is required to optimise the oxide removal, however the effects of alternate temperatures on the desorption process effects the reaction kinetics. By using selected bias imaging, scanning tunnelling microscopy (STM) can be used to probe the underlying bulk whilst the native oxide is still present. Hence the effects of oxide removal on the surface can be identified during the native oxide desorption. By comparing Ga assisted oxide removal on both vicinal and off cut samples, the Ga adatom kinetics are shown to underpin the oxide removal process and a sample temperature in excess of 500 °C is necessary to optimise the procedure.