Industry plays as a double-edged sword that can contribute to both gross domestic product (GDP) and pollution, thus the concept of eco-industrial development which emphasize the environmental cleanness in economy development has received more and more attentions recently. Different from the traditional development mode which merely relocating industries outside of the cities for pursuing sustainable development, eco-industrial development makes significant innovation by treating or utilizing wastes (i.e. solid wastes and waste energy) in a smart way for local industries to achieve a win-win situation. In order to investigate the eco-benefits of eco-industrial development in China, this study focused on an industrial and urban symbiosis case of Guiyang city in which process synergy, municipal solid wastes recycling and waste energy utilization were incorporated in this typical industrial city. This city is resource-dependent, has many heavy industries, and these severely hinder sustainable development in this city. In order to promote eco-industrial development, an integrated coal, electricity, aluminum, phosphor chemical, iron/steel industry and urban symbiosis network was firstly designed, with linkages between various industries through energy exchanges and process synergies. Subsequently, a quantitative assessment on the life cycle environmental benefits were further conducted. Then, we found that a dramatic resource saving and carbon dioxide emission reduction can be achieved. Finally, some policy implications to address the barriers of promoting industrial and urban symbiosis were proposed. This study is critical for future industrial and urban planning policy making and shed a light on innovative eco-industrial development in China.