Bicycloalkanes with the potential for deployment in high-density diesel and jet fuels can be conveniently generated from cycloolefins using a two-step profess. Dimerization of the cycloolefin may be affected, catalytically; using commercially available Fe(III) salts, and the reaction is tolerant of ring size (C-5-C-8) and limited ring-substitution patterns. Generation of an allylic radical is strongly suggested; however, observation of Fe-catalyzed olefin rearrangements and transfer dehydrogenation reactions may implicate the involvement of discrete organometallic complexes in the reaction. The fully Saturated bicycloalkanes are easily prepared via metal-catalyzed hydrogenation of the Cycloolefin-cycloalkane dimeric species.