At present, there exists a lack of an in-depth study on the quality of service evaluation of computer systems from the perspective of user psychological experience. This paper proposes an overall model for prediction of user psychological experience which is based on the environmental analysis of E-learning, the quantitative evaluation of user psychological experience and emotion. First, this study analyzes the impact of usability, usefulness, emotion and other factors on the psychological experience of E-learning users. Next, we use the resource coverage rate, recommendation hit rate and other indicators to measure usability and usefulness that are to construct the feature weight matrix and then use the AHP to quantify the overall user psychological experience evaluation model. The partial least squares regression method is adopted to take the individual characteristics of the learners as independent variables, and the characteristics of negative emotion regulation strategies as the variables. The proposed model can effectively find the E-learning system experience in the shortcomings of user psychology through a practical application. The results of this study can be used to build a more suitable quantitative evaluation method of user psychological examination for further study the characteristics of emotions affecting the user’s psychological experience.