Various forms of sulfonic acid (SO 3 H) functionalized cellulose-based heterogeneous catalysts were prepared, and their properties on glycerol acetylation reactions to mono-, di-, and triacetin products were investigated. Superior catalytic activity and stability for the reactions was observed on SO 3 H-NDOC catalyst that is obtained by (i) crosslinking of the cellulose units with epichlorohydrin into a three-dimensionally-networked deoxycellulose-matrix and (ii) sulfonic acid functionalization on the crosslinked deoxycellulose support via CS atomic linkages (CSO 3 H). It was found that sulfonic acid functionalization via an ether type OS atomic linkage (COSO 3 H) or the direct utilization of the pristine cellulose support without a fortification by crosslinking led to significant deactivation of the catalysts by substantial acidity loss. The intrinsic glycerol conversion turnover rate on SO 3 H-NDOC was comparable to that of commercial Amberlyst-15 solid resin, demonstrating the effectiveness of this renewable cellulose-derived heterogeneous catalyst for glycerol acetylation to fuel additives.