The synthesis of benxyl propinate with the crystal ball supported nano-sized SO2-₄/TiO_2solid superacid as catalysts was studied, including esterification conditions and effect of repeated use of the catalyst. Under optimum synthesis condition, the conversion rate of propionic acid is 97.5%. As a result, after the catalyst is used repeatedly for five times (3.0h one time), the 3.0h conversion rate of propionic acid becomes down to 90.3% for the esterificational reaction of propionic acid and alpha-hydroxytoluene. The selectivity of catalyst is good and no by products were formed by gas chromatography. It is excellent for the synthesis of benxyl propinate.