The demand for renewable resources, surplus availability, low cost and lower environmental impact has led to the utilization of bio-glycerol into high-value derivatives and functional chemicals for sustainability of the bio-diesel industry. The production of bio-fuel additives is of great interest as there is a gradual shift from petro-based chemicals to green chemicals. This work involves the direct synthesis of oxygenated fuel additives, 1,3-dioxalane and 1,3-dioxane from glycerol and benzyl alcohol over FeCl3/MCM-41 catalyst. The reaction progresses successfully to produce 1,3-dioxalane primarily by in-situ oxidation of benzyl alcohol to benzaldehyde and subsequent condensation reaction of benzaldehyde with glycerol. Glycerol primarily acted as green solvent to facilitate the oxidation of benzyl alcohol to benzaldehyde and as a fuel additive precursor to produce 1,3-dioxalane in the preceding reaction. FeCl3/MCM-41 catalyst presented high performance achieving 92% glycerol conversion with 75% selectivity to 1,3-dioxalane in a reaction performed at 100 degrees C for 60 min. (C) 2020 Elsevier Ltd. All rights reserved.