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The majority of contemporary methods of analyzing critical components are commonly based on failure data, however, for the electronic products which own a long life-span and high reliability, low or even zero-failure is a technical puzzle for reliability assessment. In this paper, on the idea of FMMEA, a new approach of determining critical components based on the theory of PoF (Physics of Failure) is proposed. Through the simulation by EDA software, the outputs of electronic systems of different components at different failure threshold values are obtained. Those of greater value have been picked out. On basis of the failure mechanisms of various components, the degradation models of the components are established firstly. Through experiments the degradation parameters are determined then. The Monte-Carlo and Worst-Case analysis are carried out by making use of the obtained degradation formula. After that, the critical components can be determined. This approach can find out the weaknesses of electronic systems and quantitatively present the effects on electronic systems of components' degradation, which can provide theoretical support for the follow-up work of reliability.