In this study, a method consisting in coupling transesterifications for no-glycerol biodiesel production catalyzed by CaO was put forward. The transesterification between rapeseed oil and methanol was greatly improved by integrating glycerol and dimethyl carbonate (DMC) transesterification. From this result, it was found that the high fatty acid methyl ester (FAME) yield of 92.6% (with ultra-traces of glycerol as a by-product) was obtained at 65°C under normal pressure, which is as high as the previously reported supercritical DMC method for no-glycerol biodiesel production at a reaction temperature of 350°C and under pressures up to 17.8MPa. Moreover, this new method has high water tolerance, and a yield of over 82% of FAME is still achieved in the presence of 0.2% of water. The optimized reaction conditions, such as the molar ratio of DMC to methanol, the catalyst dosage and the reaction time, were investigated to produce high-quality biodiesel. The fuel properties determined and discussed in light of EN 14214 (European standards) demonstrate that the biodiesel produced using this new method has good flow properties with a cloud filter plugging point of –10°C and a pour point of –9.4°C. Furthermore, the amount of free glycerol was found to be as low as 0.018% in the biodiesel obtained directly from this new method without any further processing. The results of this study indicate the feasibility of producing quality biodiesel fuels without glycerol by coupling transesterifications.