Photoluminescence properties of nominally undoped ZnO thin films grown by radical-source molecular-beam epitaxy have been investigated as a function of (i) sample growth conditions, (ii) excitation laser power density, and (iii) measurement temperatures. Altogether four excitonic emission peaks were observed at photon energy of 3.3646, 3.3606, 3.3572, and 3.3331 eV, which are tentatively denoted as emission peaks A, D, F, and G, respectively. We have classified the defect types responsible for the emission peaks into the following two groups; (i) D and F, whose responsible defect types are suggested to be residual impurities such as aluminum and indium, respectively, and (ii) A and G, whose responsible defect types are suggested to be intrinsic defects such as oxygen vacancies, interstitial zinc, and extended structural defects particularly for G. (c) 2005 American Institute of Physics.