Novel mesoporous gallosilicates with tuned hydrophobicity were synthesized through methylation of extra small XS-SiO2 silica particle via condensation with trimethoxymethylsilane CH3Si(OCH3)3 followed by impregnation with gallium (III) precursors. The structural and textural properties of the solids obtained were extensively characterized by different techniques. The synthesized catalysts displayed excellent catalytic activity in the acetalization of acetone with glycerol to produce solketal. Among all the studied catalysts, the most active catalyst, XS-10 %Me-GaLac, displayed high turnover number and significantly improved glycerol conversion which is attributed to the relatively hydrophobic surface and high amount of accessible active acid sites. The high acidity and enhanced hydrophobicity of this catalyst was generated by the incorporation of the methyl groups which allowed a homogeneous dispersion of highly active gallium species on the silica matrix before calcination. The effect of reaction time, temperature, catalyst loading and acetone to glycerol molar ratio was investigated. Furthermore, the mesoporous gallosilicate materials were truly heterogeneous without leaching gallium active sites and can be efficiently reused in successive catalytic cycles.