In order to meet energy and environmental challenges, many countries will implement the replacement of fuel vehicles for the future clean energy transition; so, the number of electric vehicles (EVs) operating in cities will grow significantly. It is crucial to assess the risks of the electric vehicle supply chain (EVSC) and prevent them. Based on this, this paper proposes an EVSC risk research framework with combined weights and an improved matter-element extension model: (i) Firstly, the EVSC evaluation index system is constructed from the six stages of supply chain planning, sales, procurement, manufacturing, distribution, after-sales, and external risks. (ii) The subjective and objective weights are calculated by the decision laboratory method and entropy weight method, respectively, and then the minimum deviation method is used for a combined design to overcome the defects of a single method. (iii) An improved matter-element extension model (MEEM) is constructed by introducing asymmetric proximity degree and risk bias. (iv) The model is applied to a case study and its feasibility and superiority are verified through sensitivity analysis and comparative analysis. The final results show that the method and framework proposed in this paper are in line with EVSC risk assessment standards and superior to other models, which can help EVSC managers to identify potential risks, formulate appropriate risk prevention measures, promote the stable development of electric vehicles, and provide a reference for the development of energy and environment.