The hydrogenation of ethylene, l-butene, and 1,3-butadiene has been used as a probe reaction in an attempt to monitor any possible changes in catalytic behavior induced by supporting nickel on different types of graphite nanofiber support materials. This study is designed to compare the catalytic behavior of the metal particles when dispersed on three types of nanofibers, where the orientation of the graphite platelets within the structures is significantly different in each case. The metal crystallites are located in such a manner that the majority of particles are in direct contact with graphite edge regions. It should be emphasized, however, that there are subtle differences in the spacing between adjacent exposed carbon atoms in the various nanofiber structures. As a consequence, it is highly probable that the atomic arrangement of the surfaces of nickel particles that nucleate on these different graphite edges will be dictated to a large degree by the interaction with the atoms in nanofiber supports. Under such circumstances one might reasonably expect that different crystallographic faces of nickel will be exposed to the reactant gas depending on which type of nanofiber structure is used as the supporting medium. For comparison purposes, the same set of hydrogenation reactions were carried out under similar conditions over gamma-alumina supported nickel particles.