With the increasingly serious employment situation in China, the government and schools encourage college students to start businesses to alleviate employment pressure. College student's successful entrepreneurship depends on national preferential policies, social support, and, most importantly, their healthy and solid psychological quality and entrepreneurial psychological quality. The purpose is to understand the entrepreneurial psychology of college students and study the entrepreneurial psychological effect. Firstly, the four aspects of entrepreneurial psychology are summarized, including entrepreneurial awareness, entrepreneurial volition, entrepreneurial ability, and entrepreneurial personality. Secondly, the research status of college students' entrepreneurial psychology is reviewed, and the existing problems are pointed out. Thirdly, the combined model of wavelet transform and Neural Network (NN) is proposed, and the feasibility of the proposed model is evaluated through the analysis of college students' entrepreneurial psychology. The wavelet NN is used in experimental design to predict college students' entrepreneurial psychology, and the predicted results are compared with the actual value. From the perspective of the prediction results of entrepreneurial psychology, the combination of wavelet algorithm and neural network is more accurate for entrepreneurial psychology prediction and evaluation results of law students. Overall, the difference between the predicted value and the actual value is within 0.3 points, which is relatively stable. According to the analysis of single-factor results, the scores of students of different majors in the four dimensions of entrepreneurial psychology are all higher than 3.5, but there is no significant difference among the four dimensions (P > 0.05), indicating that the major has no significant impact on entrepreneurial psychology; law students with different educational backgrounds have significant differences in entrepreneurial psychology (P < 0.05), among which students with a master's degree have the strongest entrepreneurial will, while doctoral students have the lowest entrepreneurial will; in terms of entrepreneurial psychological capital, men's self-efficacy is higher than women's, and the difference is significant (P < 0.05). The difference between males and females in the scores of entrepreneurial psychological factors' four aspects is not very obvious. In terms of entrepreneurial psychological capital, males' self-efficacy is significantly higher than females' (P < 0.05). Artificial Intelligence (AI) technology has great application prospects in the prediction and evaluation of college students' entrepreneurial psychology, and college students' entrepreneurial psychology is highly correlated with gender and education.