With the development of human resource management, the function of human resource becomes more prominent in performance management in enterprises. By using strategic and coherent approach, we can measure the performance of employees which individually and collectively contribute to the achievement of the objectives of the business. Because human resource management (HRM) is a multiple dimensional system, the HRM performance evaluation should be taken peer variables into account. So, we proposed a peer appraisal method, denoted as TOPSIS, to evaluate the performance of human resource in enterprises. Before we applied TOPSIS methodology, the indexes for measuring the HR performance should be identified firstly. Based on the basic traits of HRM, the indexes are identified by grey correlation analysis. A peer performance evaluation frame based on grey theory and TOPSIS methodology is proposed in this paper. Using the HRM performance evaluation frame, we applied in 45 scientific material enterprises in Jilin province and drew corresponding constructive conclusions.