ZnO thin film was grown on a sapphire single crystal substrate by plasma assisted molecular beamepitaxy. In addition to near band edge (NBE) emissions, both blue and green luminescences are also observedtogether. The PL intensity of the blue luminescence (BL) range from 2.7 to 2.9eV increased as the amountof activated oxygen increased, but green luminescence (GL) was weakly observed at about 2.4eV without muchchange in intensity. This result is quite unlike previous studies in which BL and GL were regarded as thetransition between shallow donor levels such as oxygen vacancy and interstitial zinc. Based on the transitionlevel and formation energy of the ZnO intrinsic defects predicted through the first principle calculation, whichemploys density functional approximation (DFA) revised by local density approximation (LDA) and the LDA+Uapproach, the green and blue luminescence are nearly coincident with the transition from the conduction bandto zinc vacancies of V2-Zn and V-Zn, respectively.