Bioenergy supply chains can offer social benefits. In most related research, the total number of created jobs is used as the indicator of social benefits. Only a few of them quantify social benefits considering the different impact of economic activities in different locations. In this paper, a new method of measuring the social benefits of bioethanol supply chains is proposed that considers job creation, biomass purchase, and the different impacts of economic activities in different locations. A multi-objective mixed integer linear programming (MILP) model is developed to address the optimal design of a bioethanol supply chain that maximizes both economic and social benefits. The ε-constraint method is employed to solve the model and a set of Pareto-optimal solutions is obtained that shows the relationship between the two objectives. The developed model is applied to case studies in Liaoning Province in Northeast China. Actual data are collected as practical as possible for the feasibility and effectiveness of the results. The results show that the bioethanol supply chain can bring about both economic and social benefits in the given area and offers governments a better and more efficient way to create social benefits. The effect of the government subsidy on enterprises’ decisions about economic and social benefits is discussed.