The standard (p ∘ =0.1MPa) molar enthalpy of formation for gaseous 2-phenylbenzimidazole (2-PhBIM) and 2-benzylbenzimidazole (2-BzBIM) were derived from the standard molar enthalpies of combustion, at T=298.15K, measured by static bomb calorimetry, and the standard molar enthalpy of sublimation, at T=298.15K, measured by Calvet microcalorimetry in the case of 2-phenylbenzimidazole or derived from the variation of the vapour pressures, determined by the Knudsen effusion technique, with temperatures between (393 and 412)K for 2-benzylbenzimidazole. Heat capacities, in the temperature ranges from (268.15 to 322.10)K for 2-phenylbenzimidazole and (270.15 to 316.02)K for 2-benzylbenzimidazole, were also measured with a differential scanning calorimeter. ΔcHm∘(cr)/kJ·mol-1ΔcrgHm∘(T=298.15K)/kJ·mol-12-Phenylbenzimidazole (2-PhBIM)−6679.8±0.9123.0±1.72-Benzylbenzimidazole (2-BzBIM)−7327.1±4.0136.2±0.5