The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${alpha}$,${eta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${sigma}$ constants with a negative value of reaction constant. The ${ ho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.