Abstract Dehydrogenation or oxidative dehydrogenation (ODH) of alkanes to produce alkenes directly from natural gas/shale gas is gaining in importance. Ti3AlC2, a MAX phase, which hitherto had not been used in catalysis, efficiently catalyzes the ODH of n-butane to butenes and butadiene, which are important intermediates for the synthesis of polymers and other compounds. The catalyst, which combines both metallic and ceramic properties, is stable for at least 30?h on stream, even at low O2:butane ratios, without suffering from coking. This material has neither lattice oxygens nor noble metals, yet a unique combination of numerous defects and a thin surface Ti1?yAlyO2?y/2 layer that is rich in oxygen vacancies makes it an active catalyst. Given the large number of compositions available, MAX phases may find applications in several heterogeneously catalyzed reactions.