Policy communication network structure can be taken as a result and as a target of policy communication on social media. This study explores the communication network of the Mass Entrepreneurship and Innovation policy on social media, using social network analysis, to investigate the relationships that were constructed as a result of policy-related interactions, through visual and quantitative means. The results revealed that the entire network structure comprised a relatively concentrated interactive group, some numerous scattered subgroups, and independent nodes, with policy audiences playing an integral and crucial role. In the core network structure, different user nodes had differential influences in the policy network structure. Nodes associated with government sectors and media played relatively important roles in expanding the scope of communication and displayed more advantages in deepening interaction. These findings have implications for the effective communication of policies. Measures should be adopted to avoid or minimize negative impacts in the policy communication on social media.