The purpose of this research is to test the mediation effect of self-efficacy on college student's perception of teacher autonomy support and students' deep learning, and whether the peer support perceived by students can moderate the relationship between perceived teacher autonomy support and deep learning. A survey of 1,800 college students from a provincial undergraduate normal university in Guizhou Province in China was conducted through the revised Perceived Teacher Autonomy Support Scale, Deep Learning Scale, Self-Efficacy Scale, and Perceived Peer Support Scale (Mean age = 21 years old, SD = 1.34). Data use SPSS23.0, AMOS22.0 for descriptive analysis and correlation analysis, exploratory factor analysis (EFA) and confirmatory factor analysis (CFA), moderation effect, and mediation effect analysis. The research results show that after controlling for gender, major, and grade, self-efficacy partially moderates the connection between perceived teacher autonomy support and deep learning of college students. Moreover, perceived peer support mediates the relationship between perceived teacher autonomy support and students' self-efficacy.