High energy electron irradiation (HEEI) effects on the as-grown and annealed ZnO thin films grown by electrochemical deposition were investigated. Both samples were exposed to the sequential electron irradiations of 6, 12 and 15MeV energies at a fluence of 1×1012e−/cm2. The results of X-ray diffraction suggest that a highly strong crystallographic structure can be produced by annealing process. Photoluminescence (PL) studies show that the EI produces violet emission which results from the zinc interstitial. Recombination lifetime (RL) values of the both films reveal that the high quality crystals are obtained. The decreasing trends of RL values with increasing electron energy have been explained by the formation of crystal defects due to the HEEI.