GaN epilayers grown by molecular beam epitaxy were photoelectrochemically (PEC) oxidized in an aqueous KOH solution. The oxidation effect was investigated by defect-related photoconductivity and photoluminescence. The PEC treated GaN show decreased extrinsic photoresponse and concentration of deep level states in comparison with the as-grown sample. The PEC process also results in enhanced donor-bound exciton photoluminescence at 3.47 eV and restrained 3.4 eV band. No strain is detected in the PEC oxidized GaN. The 3.4 eV band is related to structural defects instead of oxygen impurities. Rather, the defects can be passivated by the PEC oxidation. © 2001 American Institute of Physics.