Peer counseling is the help of trained or supervised non-professionals with the function of psychological counseling, which has the advantages and characteristics of mutual assistance, acceptability and extensiveness, and has been highly valued by colleges and universities in recent years, however, less attention has been paid to the evaluation of the effect of peer counseling and the empirical research is still in a gap. In this regard, this paper makes an innovative attempt to integrate affective computing technology into peer counseling, aiming to improve the competence, interpersonal ability and psychological adaptation quality of peer counselors through affective identification, affective analysis and affective feedback. The effectiveness of the integration design of affective computing and peer counseling was empirically examined with 73 freshman peer counselors as the research subjects. The empirical results showed that the peer counselors supported by affective computing technology significantly outperformed the traditional peer counseling effects in the dimensions of competence, interpersonal competence, and psychological adaptive quality (P>0.05). The results of this study not only provide a new tool for peer psychological counseling in colleges and universities, but also provide valuable experience for the application and validation of affective computing technology in complex, real-world human-computer interaction scenarios.