Furfural is only derived from lignocellulosic biomass and is an important chemical used in the plastics, agrochemical, and pharmaceutical industries. The existing industrial furfural production process, involving reaction and purification steps, suffers from a low yield and intensive energy use. Hence, major improvements are needed to sustainably upgrade the furfural production process. In this study, the conventional furfural process based on a continuous stirred tank reactor and distillation columns was designed and optimized from an actual aqueous xylose solution via a biomass pretreatment step. Subsequently, a reactive distillation (RD) and extraction/distillation (ED) configuration was proposed for the reaction and purification steps, respectively, to improve the process efficiency. RD can remove furfural instantly from the reactive liquid phase and can separate heavy components from the raw furfural stream, while the ED configuration with toluene and butyl chloride used as extracting solvents can effectively separate furfural from a dilute aqueous stream. The results showed that the hybrid RD-ED process using a butyl chloride solvent saves up to 51.8% and 57.4% of the total investment costs and total annual costs, respectively, compared to the conventional process. Furthermore, environmental impacts were evaluated and compared for all structural alternatives.