ZnO thin film was grown on a sapphire single crystal substrate by plasma assisted molecular beam epitaxy. In addition to near band edge (NBE) emissions, both blue and green luminescences are also observed together. The PL intensity of the blue luminescence (BL) range from 2.7 to 2.9 eV increased as the amount of activated oxygen increased, but green luminescence (GL) was weakly observed at about 2.4 eV without much change in intensity. This result is quite unlike previous studies in which BL and GL were regarded as the transition between shallow donor levels such as oxygen vacancy and interstitial zinc. Based on the transition level and formation energy of the ZnO intrinsic defects predicted through the first principle calculation, which employs density functional approximation (DFA) revised by local density approximation (LDA) and the LDA+U approach, the green and blue luminescence are nearly coincident with the transition from the conduction band to zinc vacancies of $V^{2-}_{Zn}$ and $V^-_{Zn}$, respectively.