Here we report a green approach for the production of renewable cyclic-oxygenates useful for fuel additive application, by the acetalization reaction of bioderived glycerol with furfural over an efficient bifunctional −SO 3 H/C−Si−Zr catalyst developed in our laboratory. The catalyst exhibited 100% conversion with 100% selectivity to cyclic-oxygenates (1,3-dioxane & 1,3-dioxolane) at room temperature even with solvent-free reaction conditions, which is the highest-ever reported so far, to the best of our knowledge. This can be attributed to the superior catalytic properties of the −SO 3 H/C−Si−Zr catalyst such as high surface area, ordered mesoporosity, and an appropriate combination of Lewis and Bronsted acidity facilitated by the molecular level interaction among C, Si, and Zr during the simultaneous carbonization, sulfonation, and metal-functionalization of bioglycerol. The process successfully utilized the waste biodiesel-derived glycerol to produce ∼100% yield biodiesel additives, which in turn achieved the 100% yield of the biodiesel product and the overall economy of the biodiesel industry.