It is known that angle-resolved x-ray photoelectron spectroscopy (ARXPS) provides, in addition to ordinary XPS information, quite new information concerning the crystal regularity of the surface layers. This technique was used to characterize the initial crystal growth of gold films evaporated on GaAs (110) surfaces to a thickness about 5-6Å. The angular distribution curve (ADC) of Au 4f photoelectron intensity showed some clear fine structure after the heat treatment for 30 minutes at 350-400°C. Taking the results of chemical state analysis into consideration, it can be concluded that the Au atoms grew epitaxially in an island-like fashion. When the annealing temperature was raised over 450°C, the fine structure of ADC from the Au 4f peak disappeared, implying diffusion of Au atoms into the bulk GaAs crystal. In summary it is shown that ARXPS has quite useful applicability for investigation of the initial crystal growth of very thin films evaporated on semiconductor surfaces.