In China, entrepreneurship education and innovation activities are regarded as essential directions of higher education reform. Many studies explore the relationship in the existing literature, but from the individual, family, school, and society. As far peer group is concerned, the studies remained sparse especially in the context of China. To address the gap, the current study explores the relationship between peer effect and students’ intention to participate in entrepreneurship and innovation activities using 1066 undergraduate students from Nanjing Agricultural University, China. The study employed ordinary least square (OLS) regression and revealed that college students' social networks have more substantial and irreplaceable effects on other students. Moreover, the current study also employed mediation analysis with the fact that it is believed that peer effect can influence college students’ intention through example effect (by setting an example of excellent students for other students) and knowledge spillover effect (transmitting the information regarding new opportunities associated with entrepreneurship and innovation). In conclusion, the outcome reveals that peer effect significantly improves the students’ intention to participate in entrepreneurship and innovation activities. The example effect and knowledge spillover effect significantly mediate the relationship. The overall findings provide guidelines for institutions to strengthen the activities for peers acquainted at the university to cultivate their practical abilities and boost their intention towards participation in entrepreneurship and innovation activities.