Abstract: TiSiW₁₂O₄₀/TiO₂ was used as catalyst for the esterification of propionic acid with ethanol, propanol, butanol, n-amyl alcohol and iso-amyl alcohol. The effects of the molar ratio of alcohol to propionic acid, the amount of the catalyst, and the reaction time on synthesizing propionates were investigated. A suitable condition for synthesizing propionates was obtained, that is, the molar ratio of alcohol to propionic acid is 1.3:1, the mass ratio of the catalyst used to the reactants 2.0%, and the reaction time 1.0 h. Under this condition, the yield of ethyl propionate is 50.3%, n-propyl propionate 71.4%, n-butyl propionate 93.0%, n-amyl propionate 96.7% and iso-amyl propionate 76.2%.