Abstract: The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4- diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of (2) gave mostly 1,2,4- triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6- dimethylpyridine and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-1-yl)-2,4,6- trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of (2) in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to (2) has been observed and preliminary laser flash photolyses of (2) and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The o served transients are explained as arising from the first excited states of the pyridinium salts rather than from (1). Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five p electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.