The effect of an impurity as a donor or an acceptor in ZnO film is determined by its distribution in ZnO lattice. In this paper the distribution of Li is investigated by X-ray diffraction (XRD) and photoluminescence (PL). It is found that Li-doped ZnO films own different dependence on heat treatment temperature by contrast with pure ZnO films. For Li-doped ZnO films, although the crystallinity is promoted after heat treatment at 500oC, it is impeded effectively after heat treatment at 600oC. The abnormal phenomenon implies that Li preferential inhabits at Zn-sublattice to form a substitutional defect as an acceptor unless Li content exceeds its solubility in Zn-sublattice. The change of the PL spectra of pure ZnO films after heat treatment at different temperatures reveals that the PL peak at 650nm origins from interstitial defects. Moreover, with the increase of Li content, the intensity of the peak at 650nm decreases firstly and then increases again. This interesting changing trend further reveals that superfluous Li will enter into the octahedral interspaces as donors. As a conclusion it is proposed that it is difficult to obtain high conductive p-ZnO by monodoping of Li.