As a combination of both concepts of innovation and environmental development, green innovation is of great significance to the sustainable development of the country and industry. Previous literatures have found the separate roles of green entrepreneurial orientation and inter-organizational learning in understanding green innovation issues. However, few studies have done a comprehensive analysis of integrating three streams of research: green entrepreneurial orientation, green innovation and supply chain learning capability. Based on the resource-based view and dynamic capability theory, we examine the direct of green entrepreneurial orientation on green innovation as well as indirect effect through the mediation of supply chain learning capability. Meanwhile, an empirical data set of 228 manufacturing companies in China (Shaanxi, Guangdong, Hebei, Jiangsu, and Shandong) was used to test our hypotheses. Findings from our empirical study suggest that supply chain learning capability partially mediates the positive relationships between green entrepreneurial orientation and its two consequences—green incremental innovation and green radical innovation. In addition, this research implies that when enterprise has a strong green entrepreneurial orientation, the enterprise should make an effort to enhance the level of supply chain learning capability so as to fully develop their green innovation.