The sulfurization efficiency of 25 3-substituted-1,2,4-dithiazole-5-ones and 5-thiones towards triphenyl phosphite in acetonitrile, DCM, THF and toluene at 25 °C was evaluated. All the 1,2,4-dithiazoles are much better sulfurizing reagents than commercially available agents (PADS, TETD, Beaucage's reagent). The most efficient sulfurizing agents in all solvents are 3-phenoxy (4), 3-phenylthio (5) and 3-ethoxy-1,2,4-dithiazole-5-one (1) whose reactivity is at least two orders of magnitude higher than that of other 1,2,4-dithiazoles. Contrary to a previous report, the sulfurization with 1 does not yield carbonylsulfide and ethyl cyanate as the additional reaction products but unstable ethoxythiocarbonyl isocyanate which has been trapped with 4-methoxyaniline. Similar trapping experiments have proven that the site of attack is at the sulfur adjacent to the CO group for compounds 4 and 5. The reaction pathway involves rate-limiting initial nucleophilic attack of the phosphorus at sulfur followed by decomposition of the phosphonium intermediate to the corresponding phosphorothioate and isocyanate/isothiocyanate species. The existence of the phosphonium intermediate during sulfurization of triphenyl phosphine with 3-phenyl-1,2,4-dithiazole-5-thione (7a) was proven using kinetic studies. From the Hammett and Brønsted correlations and from other kinetic measurements it was concluded that the transition-state structure is almost apolar for the most reactive 1,2,4-dithiazoles whereas a polar structure resembling a zwitter-ionic intermediate may be more appropriate for the least reactive 1,2,4-dithiazoles. The extent of P–S bond formation and S–S bond cleavage is very similar in all reaction series but it gradually decreases with the reactivity of the 1,2,4-dithiazole derivatives.