Multi-walled carbon nanotubes (MWNT), before and after different oxidative treatments and hence possessing different oxygen surface groups, were used as catalysts for the oxidative dehydrogenation of ethylbenzene (ODE), and their performances compared to those of activated carbon and graphite samples. MWNT are active catalysts for ODE and show the highest specific activity per initial surface area amongst all the materials tested in this study. Moreover, the main advantage of using MWNT over activated carbons is their higher stability under oxidative conditions. It was shown that pre-oxidised MWNT are more active for ODE during the initial stages of the reaction, highlighting the importance of oxygenated surface groups.