We have investigated photoluminescence properties of ZnO and Zn0.95Mn0.05O thin films at 10 K grown on a (0001) ZnO crystal substrate by pulsed laser deposition. The structural characterization with x-ray diffraction and atomic force microscopy demonstrates the pseudomorphic growth of the Zn0.95Mn0.05O thin film and the atomically smooth surface. It has been found that a photoluminescence band originating from the d-d transition of Mn2+ in the Zn0.95Mn0.05O thin film appears in the energy region of deep-level transitions in a ZnO crystal: The photoluminescence-decay time is in the order of sub-milliseconds. The photoluminescence-excitation spectrum of the Mn-related transition exhibits a peaky structure with a broad profile at the energy lower than the A-exciton energy by ∼100 meV. This indicates that the light incorporation of Mn to ZnO leads to a negative energy shift of the band-gap energy. The broad profile of the band-edge transition observed in the photoluminescence-excitation spectrum suggests that the incorporation of Mn produces remarkable random-potential fluctuations.