Owing to significant environmental and economical concerns of fossil fuels, the search for alternative renewable fuels has received a explicit research interest in recent times. In this work, we prepared efficient solid acid catalysts, namely, SnO2, WO3/SnO2, MoO3/SnO2, and SO42-/SnO2 for the production of bioadditive fuels from bioglycerol under ecofriendly conditions. The synthesized samples were meticulously analyzed by means of X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller (BET) surface area, Barrett-Joyner-Halenda pore size distribution, Fourier transform infrared (FT-IR) spectroscopy, FT-IR analysis of adsorbed pyridine, NH3-temperature programmed desorption, and other techniques. The catalytic efficiency of these solid acids was investigated for esterification and acetalization of glycerol with acetic acid and benzaldehyde, respectively. Characterization studies revealed that the textural properties (crystallite size and BET surface area) of pristine SnO2 were outstandingly improved after the addition of promoters to it. Remarkably, large amounts of acidic sites were found for promoted SnO2 samples as compared to pristine SnO2, attributed to a synergetic effect between SnO2 and promoters. The SO42-/SnO2 sample shows superior concentration of acidic sites accompanied by adequate superacidic sites. Concurrently, the promoters showed a favorable effect on the catalytic performance of pristine SnO2 toward glycerol valorization. The observed activity order for both esterfication and acetalization of glycerol was SO42-/SnO2 > MoO3/SnO2 > WO3/SnO2 > SnO2. The high activity of the SO42-/SnO2 is due to the presence of enhanced acidic sites, along with ample superacidic sites. Interestingly, the activity of SO42-/SnO2 catalyst was decreased with repeated use due to the reduced concentration of acidic sites along with leaching of sulfur content, decreased BET surface area, and formation of larger crystallites. © 2014 American Chemical Society.