We have investigated, both theoretically and experimentally, the reactions of naphthylium C10H7+ and d-naphthylium C10D7+ ions with H2 and D2. Cross sections as functions of the collision energy have been measured for a variety of reaction channels. Theoretical calculations have been carried out at the density functional theory level which utilizes the hybrid functional B3LYP and the split-valence 6-31G* basis set. The key features of the potential energy surfaces and the relevant thermochemical parameters have been calculated and they provide insights on the reaction mechanisms. The bimolecular reactivity of C10H7+ with H2 is dominated by the production of naphthalene cation C10H8+. The reaction is not a direct atom-abstraction process, but instead it proceeds via the formation of a stable intermediate complex C10H9+ of sigma type geometry, with a significant mobility of hydrogen along the ring. This mobility allows the scrambling of the hydrogen atoms and causes the successive statistical fragmentation of the complex into a variety of product channels. Elimination of one H(D) atom appears to be favored over elimination of one H2 or HD molecule. Alternatively, the intermediate complex can be stabilized either by collision with a third body or by emission of a photon.