The rate of thiophene decomposition was shown to be independent of the type of chalcogens used in catalysts МоХ 2 /Al 2 O 3 , where Х = S, Se. On the contrary, the rate of selenophene decomposition was shown to be higher on catalysts MoSe 2 than that on MoS 2 . This observation suggests that the decomposition proceeds on anion vacancies. The decomposition of either thiophene over MoSe 2 or selenophene over MoS 2 results in the formation of partially substituted chalcogenides. At that, the molar ratios of the substituted chalcogen to Mo were shown to coincide in both cases. The fact that the rate of the thiophene decomposition does not depend on the degree of anion exchange indicates that the decomposition is not associated with hydrogenolysis.