A novel, integrated process for economical high-yield production of D-mannose and ethanol from coffee residue waste (CRW), which is abundant and widely available, was reported. The process involves pretreatment, enzymatic hydrolysis, fermentation, color removal, and pervaporation, which can be performed using environmentally friendly technologies. The CRW was pretreated with ethanol at high temperature and then hydrolyzed with enzymes produced in-house to yield sugars. Key points of the process are: manipulations of the fermentation step that allowing bioethanol-producing yeasts to use almost glucose and galactose to produce ethanol, while retaining large amounts of D-mannose in the fermented broth; removal of colored compounds and other components from the fermented broth; and separation of ethanol and D-mannose through pervaporation. Under optimized conditions, approximately 15.7 g dry weight (DW) of D-mannose (approximately 46% of the mannose) and approximately 11.3 g DW of ethanol from 150 g DW of ethanol-pretreated CRW, were recovered.