How to find out the vulnerability and the potential failure mode in supply chain, then evaluating them means much to the protection and controlling of supply chain risks. Based on the supply chain reference operation model SCOR, this paper first gets the evaluation index system and the corresponding potential failure mode, then combined with the fuzzy set theory and grey relational theory, constructs evaluation model of supply chain vulnerability considering the index weight of all levels and the decision factors weight, and finally uses the evaluation model into some enterprises for empirical study. The result shows that the model can provide practical process guidance for enterprise in supply chain vulnerability evaluation and have practical value in management of supply chain vulnerability.