Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${Delta}H^{ eq};=;9.62;to;11.9;kcal{cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${Delta}S^{ eq};=;-34.1;to;-44.9;cal{cdot}mol^{-1}{cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.