This article combines machine intelligence-assisted gaze analysis to construct a student psychological evaluation system, which provides a basis for solving student psychological evaluation methods. At the same time, by recognizing students’ behavioral characteristics and then their psychological characteristics, a PC-side application with multiple functions such as human-computer interaction, user data management, and physiological data display and storage has been developed. In addition, this article constructs an intelligent system structure to evaluate students’ psychology through expert diagnosis. Finally, this article evaluates the students’ psychology through the system and at the same time uses the comparative test method to evaluate the system. Experimental research shows that the student psychological evaluation system based on machine intelligence-assisted gaze analysis proposed in this paper is very close to the expert diagnosis result of student psychological evaluation.