As-doped p-type ZnO thin films were fabricated by metal organic chemical vapor deposition (MOCVD) after in situ annealing in a vacuum. The p-type conduction mechanism was suggested by the analysis of X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy. It was found that most of the As dopants in p-ZnO thin films formed As-Zn-2V(Zn), shallow acceptor complex, simultaneously, carbon impurities also played an important role in realizing p-type conductivity in ZnO. Substitutional carbon on oxygen site created passivated defect bands by combining with Ga atoms due to the donor-acceptor pair Coulomb binding, which shifted the valence-band maximum upwards for ZnO and thus increased the hole concentration. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.