The detection of islanding effect is a highly important topic for photovoltaic (PV) power system. The islanding effect occurs when the distributed power source is disconnected from the main supply while the power is still supplied in partial load area, which may injure the set maintenance personnel or damage the equipment. Combining chaotic synchronization and extension theory, this research is to propose a novel detection method to distinguish the occurrence of islanding effect based on nonautonomous Chua’s circuit. To demonstrate the effectiveness of the proposed method, this paper applies PSIM to simulate the PV power system. The experimental results show that the accuracy of the proposed method achieves 98% on islanding effect.