The passivating oxide layer resulting from a high-temperature (250 degree C in air) GaAs substrate preparation procedure has been analysed by X-ray photoelectron spectroscopy. It is shown that the protective film obtained from heating a semi-insulating substrate in clean air to 250 degree C is mainly gallium oxide whereas it is an arsenic-rich mixture of As and Ga oxides after the standard preparation procedure. At this temperature, the oxidation steady-state conditions are reached after 5 minutes of heating. The higher the passivating temperature, the lower the arsenic content of the oxide layer.