Since there is lack of deeper evaluation researches on service quality from the users' psychological perspective, approaches based on e-Learning are proposed to evaluate quantitatively the quality of e-Learning user psychological experience. Models are built from the whole user psychological experience, and the influences of the features such as ease of user, usefulness and emotion on user psychological experience are analyzed and quantified using coverage of the resources and recommend hit rate, etc. Comparison matrixes and a model to quantify all user psychological experience are constructed through the analytic hierarchy process. The experiment in a Chinese university's e-Learning system shows that the proposed approach is effective in obtaining the shortcoming of user psychological experience in e-Learning. Therefore, the proposed work framework can facilitate deeper researches on user psychological experience, such as emotion influence on user psychological experience, and offer special reference to build models to integrate user psychological experience evaluations.