Utilizing the data of China’s A-share listed enterprises from 2010 to 2022, this study constructs a cross-linked connection network based on supplier-customer relationships and examines the peer effect of enterprise ambidextrous innovation in the supply chain networks. It is found that both exploitative and exploratory innovation decisions exhibit peer effects within supply chain networks. Further research shows that the peer effect of enterprise ambidextrous innovation in supply chain networks exhibits different behavioral characteristics. From the perspective of enterprises’ own network characteristics, supply chain network relationship embedding positively moderates the peer effect of exploitative innovation and negatively moderates the peer effect of exploratory innovation. Supply chain network structure embedding positively moderates the peer effect of exploratory innovation. From the macro-environmental perspective, the peer effect of exploitative innovation is more significant when the macro environmental uncertainty is high, the peer effect of exploratory innovation is more significant when the macro environmental uncertainty is low. Both the peer effect of exploitative innovation and the peer effect of exploratory innovation are more significant in the samples of non-state-owned enterprises and in industries with sluggish development prospects.