College students play an important role in higher education and future social life. Research has a significant impact on college students' self-efficacy. Taking college students in Chengdu, China as an example, this study adopts the fuzzy-set qualitative comparative analysis (fsQCA) method, comprehensively incorporating various influencing factors such as demographic characteristics, physical exercise behavior, and life satisfaction. From the perspective of physical exercise behavior and life satisfaction, an asymmetric causal model that affects college students' high self-efficacy is constructed. The research results support the main principles of complexity theory, confirming the heterogeneity and complexity of the antecedent conditions for high self-efficacy among college students. Nineteen causal condition combinations that can promote high self-efficacy among college students are obtained. This study conducts exploratory research on the introduction of complexity theory analysis into the study of college students' physical exercise, life satisfaction, and self-efficacy. It also provides a decision-making reference path for improving the life satisfaction, physical exercise behavior, and self-efficacy of college students.