The products concentrations in traditional acetone-butanol (AB) fermentation are too low that large amount of energy has to be consumed in the distillation and product recovery process. Aiming at direct utilization of the fermentation products, in this study, optimization of property-improved biodiesel manufacturing process coupled with AB extractive fermentation was conducted, under the condition of using the biodiesel originated from waste cooking oil as the extractant and high concentrated corn flour medium. The effect of biodiesel/broth volume ratio, waste supernatant recycle ratio, and electronic carrier addition on the major process performance index was carefully investigated. Under the optimized condition, the biodiesel quality was improved with the cetane value increased from 51.4 to 54.4; "actual butanol yield" reached to a level of 18%, and waste supernatant recycle ratio exceeded 50%. In this way, elimination of energy-consuming product recovery process and realization of "energy-saving & waste minimization" industrial production target advocated by the state government, could be potentially expected.