Pre-shaped hierarchical porous carbon (HPC) spheres have been synthesized through a facile anion exchanged route. An industrial polymeric anion-exchange resin with a hierarchical pore structure was used as the carbon precursor. Its high porosity was conserved using an aluminate/silicate precursor forming a hard support to prevent the structural collapse during the carbonization process. Physicochemical bulk and surface properties of the obtained HPC spheres were characterized by X-ray diffraction, scanning and transmission electron microscopy, N2 physisorption, and X-ray photoemission spectroscopy. Results obtained indicate that HPC keeps the abundant hierarchical porosity including meso- and macropores as well as the high surface area of the resin precursor. The as-synthesized HPC spheres were tested as a catalyst for oxidative dehydrogenation of ethylbenzene to styrene. The oxygen-rich catalyst surface formed under reaction conditions shows a high catalytic performance and stability, making HPC to a potential catalyst for this type of reaction.