In this study nanostructured MoO3 and WO3 promoted SnO2 solid acid catalysts were explored for the production of glycerol carbonate via carbonylation of bioglycerol with urea. The investigated reference SnO2 and promoted catalysts were synthesized by fusion and wet-impregnation methods, respectively. The physicochemical properties of the prepared catalysts were thoroughly analyzed by XRD, Raman, BET surface area, TEM, FTIR, pyridine adsorbed FTIR, NH3-TPD, and XPS techniques. It was found from the characterization studies that integration of SnO2 with MoO3 and WO3 promoters leads to remarkable structural, textural, and acidic properties. Especially, a high quantity of acidic sites were observed over the MoO3/SnO2 catalyst (~ 81.45 μmol g−1) followed by WO3/SnO2 (61.81 μmol g−1) and pure SnO2 (46.47 μmol g−1), which played a key role in the carbonylation of bioglycerol with urea. The BET specific surface area and oxygen vacancies of SnO2 were significantly enhanced after the addition of MoO3 and WO3 promoters. TEM images revealed the formation of nanosized particles with a diameter of around 5–25 nm for the synthesized catalysts. The MoO3/SnO2 catalyst exhibited a high conversion and selectivity towards glycerol carbonate in comparison to other catalysts. The observed better performance is attributed to unique properties of MoO3/SnO2 catalyst including smaller crystallite size, high specific surface area, abundant oxygen vacancies, and more number of acidic sites. This catalyst also exhibited remarkable stability with no significant loss of activity in the recycling experiments. Nanostructured MoO3/SnO2 solid acid catalyst exhibited an excellent catalytic activity and a high selectivity to glycerol carbonate in the carbonylation of bioglycerol with urea under solvent-free and mild conditions.