Microwave-assisted hydrogen transfer to anthracene and phenanthrene over Pd/C was investigated under mild conditions. The effects of reaction temperature, initial hydrogen pressure, and reaction time on the reactant conversions and product selectivities were examined. The results show that the hydrogenations of both reactants proceed at much lower temperature and hydrogen pressure under microwave irradiation than those by conventional heating and that related reactions include both mon- and biatomic hydrogen transfer. The reactivities of both reactants and their products toward hydrogenation and/or dehydrogenation are closely related to super-delocalizability and resonance energy values of the related species.