Surface pretreatment using Cl2 plasma was applied to n-type GaN and Ti/Al ohmic contacts with resistivity of ~ 10−6 Ω cm2, realized without annealing. Using synchrotron radiation photoemission spectroscopy, it was observed that the Fermi level moved by 0.5 eV toward the conduction band edge and the atomic ratio of Ga/N was increased by the treatment. This suggests that a number of N vacancies were produced at the treated surface and the Fermi level was pinned at the energy level of N vacancies near the conduction band. The N vacancies acting as donors for electrons produced a number of electrons, resulting in the near surface region to be in the degenerate state. Both the shift of Fermi level and the production of electrons at the treated surface lead to the reduction in contact resistivity through the decrease of the effective Schottky barrier for conduction of electrons.