The reaction of the substituted phenacyl bromides 1a–e and 2a–e with thioglycolic acid 3 and thiophenol 6 in methanol underwent nucleophilic substitution SN2 mechanism to give the corresponding 2-sulfanylacetic acid derivatives 4a–e, 5a–e and benzenethiol derivatives 9a–e, 10a–e. The reactants and products were identified by mass spectra, infrared and nuclear magnetic resonance. We measured the kinetics of these reactions conductometrically in methanol at a range of temperatures. The rates of the reactions were found to fit the Hammett equation and correlated with σ-Hammett values. The ρ values for thioglycolic acid were 1.22–1.21 in the case of 4-substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.39–0.35. The ρ values for thiophenol were 0.97–0.83 in the case of 4-substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.79–0.74. The Brønsted-type plot was linear with a α = −0.41 ± 0.03. The kinetic data and structure-reactivity relationships indicate that the reaction of 1a–e and 2a–e with thiol nucleophiles proceeds by a concerted mechanism. The plot of log k45 versus log k30, the plot log(kx,3-NO2/kH) versus log(kx/kH), and the Brønsted-type correlation indicate that the reactions of the thiol nucleophiles with the substituted phenacyl bromides 1a–e and 2a–e are attributed to the electronic nature of the substituents. Copyright © 2011 John Wiley & Sons, Ltd.