The oxidation process of pure GaAs has been studied with use of several complementary experimental techniques: Raman scattering, electrical conductivity, transmission electron microscopy, and secondary-ion mass spectrometry. The morphology of the oxide layer and the oxide-GaAs interface evolve as a function of oxidation time. A high density of well-oriented As microcrystallites penetrates into the substrate, forming a conductive interfacial layer in the early stages of the oxidation process. After longer oxidation times, when the Raman As intensity and the interfacial conductivity are reduced, As is distributed into the oxide layer, forming crystallites that are no longer well oriented. Simultaneously, the crystalline gallium oxide breaks up to into microcrystallites that could provide channels for the outdiffusion of As. From the experimental evidence, we deduce that the interfacial density of crystalline As is reduced for long oxidation times.