A series of naphthyl-containing compounds has been synthesized. The radical cations of these compounds were generated in solution using three independent techniques. These compounds were found to undergo bond-cleavage reactions in exact analogy to the corresponding phenyl-containing compounds. The radical cations of these compounds were also generated in the gas phase in a mass spectrometer and show the same reactivity patterns as was observed in solution. Under coal liquefaction conditions, a different reactivity pattern of these compounds has been previously observed but ascribed to reactions of radical cations. Since the radical cations of naphthyl-containing model compounds react differently than the naphthyl-containing model compounds under coal liquefaction conditions, a reinterpretation of catalyst-initiated bond cleavage mechanisms in naphthyl-containing coal model compounds should be undertaken.