The research purpose of this study was to apply the effects of physical education teaching on students' psychological capital and learning adjustment model by using structural equation model. AMOS 21.0 was used to analyze the model's, Model fitness and path analysis. The research objects were mainly students from Tai dong Junior College who took elective physical education course from October 13 to 16, 2020. A total of 120 students were tested by convenience sampling. The results showed that the model had good model fit, convergence validity and discriminant validity. The research results showed that the psychological capital of Tai-dong Junior College students had a significant influence on learning adjustment, research hypothesis was supported. The specific suggestions are to assist students in their schoolwork difficulties and provide guidance. Students should be able to relax their academic pressure and improve their physical and mental fitness by taking part in more physical activities to help students with their academic difficulties.