Defect structure of ZnO determines the optoelectronic characteristics of ZnO crystal and film. The identification and modulation of the defect structure is the foundation of the manufacture of optoelectronic devices. Although a good deal of research has been carried out about intrinsic defects and doping defects in ZnO, it is difficult to obtain a conclusive result accepted by all. In the paper, ZnO film is prepared by sol-gel method and the defect structure is expressed by photoluminescent (PL) spectroscopy. Based on some basic rules the intrinsic defect structure of ZnO is confirmed and the interaction of impurity Li and intrinsic defect is discussed. At the same time, some new electronic levels are proposed. It is surprising that although there are fourteen peaks in PL spectra of ZnO film, almost all the peaks can be identified by these basic rules.