At present, the solar photovoltaic system is extensively used. However, once a fault occurs, it is inspected manually, which is not economical. In order to remedy the defect of unavailable fault diagnosis at any irradiance and temperature in the literature with chaos synchronization based intelligent fault diagnosis for photovoltaic systems proposed by Hsieh et al., this study proposed a chaotic extension fault diagnosis method combined with error back propagation neural network to overcome this problem. It used the nn toolbox of matlab 2010 for simulation and comparison, measured current irradiance and temperature, and used the maximum power point tracking (MPPT) for chaotic extraction of eigenvalue. The range of extension field was determined by neural network. Finally, the voltage eigenvalue obtained from current temperature and irradiance was used for the fault diagnosis. Comparing the diagnostic rates with the results by Hsieh et al., this scheme can obtain better diagnostic rates when the irradiances or the temperatures are changed.