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Knowledge value chain is important for the enterprise to promote knowledge transfer. Knowledge transfer is a key link in the process of enterprise knowledge management, whose purpose is to absorb and make full use of new knowledge, and through which knowledge helpful to the enterprise is put into application to gain the competitive. The function and the dual path of knowledge value chain are analyzed, the knowledge transfer model is established based on knowledge value chain, and the performance formation and composition is interpreted in the process of knowledge transfer. Based on these mentioned above, the index system of performance evaluation of knowledge transfer is designed, the method of ELECTRE I is selected to evaluate knowledge transfer performance, and the numerical example is conducted. Therefore, the performance evaluation model, index, and method of enterprise knowledge transfer are verified scientifically.