12-Tungstosilisic acid anchored to MCM-41 was synthesized and characterized by various physicochemical techniques such as thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), laser-Raman spectroscopy, diffuse reflectance spectroscopy (DRS), N-2 adsorption-desorption, Si-29-magic-angle spinning (MAS) NMR, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The total acidity was determined by n-butyl amine titration. The types of acidic sites (acidic strength) were determined by potentiometric titration. The use of synthesized material was explored for esterification of diacarboxylic acids with butanol. Influence of various reaction parameters (catalyst concentration, acid/alcohol molar ratio and reaction time) on catalytic performance was studied. The catalyst shows high activity in terms of higher yields toward diesters, especially for dioctyl succinate and dioctyl malonate. The catalyst was also regenerated and reused for four cycles. All these characteristics imply the high potential of an environmentally benign catalyst for synthesis of succinate and malonate diesters.