Acetylation of glycerol with acetic acid was investigated over ZrO 2, TiO2-ZrO2, WOx/TiO 2-ZrO2 and MoOx/TiO2-ZrO2 solid acid catalysts to synthesize monoacetin, diacetin and triacetin having interesting applications as bio-additives for petroleum fuels. The prepared catalysts were characterized by means of XRD, BET surface area, ammonia-TPD and FT-Raman techniques. The effect of various parameters such as reaction temperature, molar ratio of acetic acid to glycerol, catalyst wt.% and time-on-stream were studied to optimize the reaction conditions. Among various catalysts investigated, the MoOx/TiO2-ZrO2 combination exhibited highest conversion ( ∼ 100%) with best product selectivity, and a high time-on-stream stability. © 2010 Elsevier B.V. All rights reserved.