Switchgrass displays an excellent potential to serve as a non-food bioenergy feedstock for bioethanol production in China due to its high potential yield on marginal lands. However, few studies have been conducted on the spatial distribution of switchgrass-based bioethanol production potential in China. This study created a land surface process model (Environmental Policy Integrated Climate GIS (Geographic Information System)-based (GEPIC) model) coupled with a life cycle analysis (LCA) to explore the spatial distribution of potential bioethanol production and present a comprehensive analysis of energy efficiency and environmental impacts throughout its whole life cycle. It provides a new approach to study the bioethanol productivity and potential environmental impact from marginal lands based on the high spatial resolution GIS data, and this applies not only to China, but also to other regions and to other types of energy plant. The results indicate that approximately 59 million ha of marginal land in China are suitable for planting switchgrass, and 22 million tons of ethanol can be produced from this land. Additionally, a potential net energy gain (NEG) of 1.75 x 106 million MJ will be achieved if all of the marginal land can be used in China, and Yunnan Province offers the most significant one that accounts for 35% of the total. Finally, this study obtained that the total environmental effect index of switchgrass-based bioethanol is the equivalent of a population of approximately 20,300, and a reduction in the global warming potential (GWP) is the most significant environmental impact.