Computational investigations on the gas-phase nucleophilic substitution reactions of p-substituted phenoxides (p-Y-C6H4O-, Y = OH, CH3O, CH3, H, F, Cl, CF3) with halomethanes (CH3X, X = F, Cl, Br, and 1) were performed by the B3LYP and MP2 methods with the 6-311+G(d,p) basis set. Calculated results indicate that the reactions are more endothermic only when the substrate is a lighter halide. The complexation enthalpies, the key parameters in the transition state (TS), the central barriers, overall barriers, overall reaction enthalpies, and the charge of the O4 atom in the TSs all present good correlations with the Hammett constants a of substituents in the nucleophile. Leffler-Grunwald rate equilibrium relationships predict the degree of bond formation in the transition state suggesting that the reactions have progressed 31%, 24%, 24%, and 21% in the TS for halomethanes (X = F, Cl, Br, and 1), respectively. The TS structure with substituents in the nucleophile is not kinetically but thermodynamically controlled, similar to the earlier results. Furthermore, the excellent relationship between the central barrier heights and the looseness of the transition state structure indicates that the stretching of the cleaving bond is one of the major factors determining the central barrier heights. The nucleophilicity of the nucleophile decreases with the increase of the electron-withdrawing power of substituent Y in the nucleophile, while the leaving-group ability of the halogen atom increases with the decrease of its Mulliken electronegativity.