The social network structure for individuals determines the quantity and quality of its taken information, however, previous experience affects his or her understanding of the information to most extent. Based on the survey data of 433 new generation migrant workers’ entrepreneurship in Henan Province, the relation between social network and entrepreneurship of new generation migrant workers is examined, the previous working experience of new generation migrant workers’ entrepreneurs and their influence on this process are discussed, and the research finds that the richer social capital is, the more developed social network is, the bigger the entrepreneurship probability of new generation migrant worker is, and that the ultimate working period and the times for changing jobs of new generation migrant workers play a positive regulating role in their social network and their entrepreneurship behaviors. China should pay attention to the construction of entrepreneurship information and knowledge channel communication so as to make more individuals of new generation migrant workers with entrepreneurship willing obtain more valuable entrepreneurship opportunities.