The core-level and valence band electronic structure of the n-GaAs (100) has been studied by synchrotron-based high-resolution photoelectron spectroscopy after irradiation by an Ar + ion beam with energy E i = 1500 eV and fluence Q = 1*10 15 ions/cm 2 . Conversion of the conductivity type of the surface layer and formation of a p-n structure has been observed. The p-surface layer thickness (d ~ 5.0 nm) and band structure were experimentally determined from the Ga3d photoelectron spectrum by separation and analysis of the low intense n-type bulk contribution from deeper layers. A band diagram of the p-n junction formed on the n-GaAs-surface by Ar + ion bombardment was reconstructed. The p-n junction proved to be unexpectedly narrow compared to the extended tail of the implanted ion depth distribution.