The study aimed at exploring how did athletes' emotional intelligence affect their responding to stress, and used players in the division II and the regular division of the public division in the 101 annual college basketball league matches as the research subjects. The study implemented convenient sampling approach to select samples; there were 700 questionnaires were distributed and 528 valid questionnaires were collected, a valid collected rate of 75.43%, after the invalid questionnaires were deducted. The researchers adopted structural equation modeling (SEM) to test the model in the study; the analyzed results showed the goodness of fit of the model is well, and the athletes' emotional intelligence positively affected their performance in coping with stress. The study also inferred the conclusions with this model that as a result of the positive evaluations given by college basketball players to emotional intelligence and stress-coping performance, and also when compared to the understandings of emotions, emotion-focused coping showed higher significance on interpersonal relationship in emotional intelligence. The findings revealed a critical issue that when training players, reinforcing the development of a positive relationship among players should be considered as a necessity by coaches other than developing skills in playing basketball.