AbstractThe utilization of biomass is a key technology toward sustainable development. Bioethanol can be used as a substitute for fossil‐based fuel and to produce commodity chemicals, in which the latter has larger benefit returns and wider application. Therefore, switching the use of bioethanol as a feedstock of chemical processes from the conventional fossil‐based one to produce large quantities of chemicals has recently received increasing attention. In this study, we investigate the potential of substituting bioethanol‐based processes for fossil‐based processes to produce ethyl acetate, by considering economic and environmental issues. Different technologies of producing ethyl acetate are considered. One representative fossil‐based process is modeled and compared with three bioethanol‐based processes, with respect to production cost and CO2 emission indicators. The results show that bioethanol‐based processes have better cost saving and less global warming potential. The identification of a feasible bioethanol‐based production process of ethyl acetate will largely contribute to the development of the chemical industry and help ensure the actual sustainability of such an emerging technology. © 2010 American Institute of Chemical Engineers Environ Prog, 2010