This report shows the rates of solvolyses for phenyl methanesulfonyl chloride (C 6 H 5 CH 2 SO 2 Cl, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride (C 6 H 5 SO 2 Cl, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ((CH 3 ) 2 CHSO 2 Cl, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an S N 2 pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ΔH ≠ and ΔS ≠ , were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in CH 3 OH/CH 3 OD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.