The surface chemistry of GaAs (100) with 50-keV Ar+ ion beam irradiation at off-normal incidence has been investigated in order to elucidate the surface nano-structuring mechanism(s). Core level and valence band studies of the surface composition were carried out as a function of fluences, which varied from 1 × 1017 to 7 × 1017 ions/cm2. Core-level spectra of samples analyzed by X-ray photoelectron spectroscopy confirmed the Ga enrichment of the surface resulting in bigger sized nano-dots. Formation of such nano-dots is attributed to be due to the interplay between preferential sputtering and surface diffusion processes. Valence band measurement shows that the shift in the Fermi edge is higher for Ga- rich, bigger sized nano-dots due to the partial oxide formation of Ga. ‘One-dimensional power spectral density’ extracted from atomic force micrographs also confirms the significant role of surface diffusion in observed nano-structuring.