The reaction of n-hexane and 1-hexene has been investigated on unsupported and supported Mo2C catalysts. Pure Mo2C catalyses the dehydrogenation and aromatization of n-hexane at and above 723 K. Benzene was formed with the highest selectivity, ∼ 65%, at 773-823 K at a conversion of ∼ 25%. Mo2C also exhibited high activity towards the reaction of n-hexane when it was deposited in a small amount (2-10%) on SiO2. It is assumed that the production of benzene occurs through the formation and subsequent dehydrogenation-Cocyclization of hexene. Catalysts prepared in situ revealed that the activation and aromatization of hexane and hexene do not require the presence of Mo-O species in the Mo2C.