In this study, a novel heterogeneous catalyst based on silicotungstic acid (STA) has been synthesised using hydrothermal and wet-impregnation methods for methanol–acetic acid esterification. Active compound STA was loaded on MCM-48 support material to compose proposed catalysis. Tungsten (W) to silica (Si) molar ratios were set as 5%, 10%, 20% and 40%. Characterizations of MCM-48 and STA/MCM-48 catalysts were performed using BET, XRD, FT-IR, DRIFT, TGA/DTA, SEM, and EDX mapping analysis. Results showed successful synthesis of the novel catalyst with good thermal stability and formation of both Brønsted acid and Lewis acid sites. The catalytic activity was also investigated in methyl acetate esterification reaction and it was shown that temperature, reaction time and the molar ratio of the reactants had significant effect on conversion rate. The highest catalytic activity was obtained as 84% with 20% catalyst at feed ratio of 1:3 (metanol:acetic acid, 353 K, 27 h).