An electrochemical process is described for the rapid and efficient conversion of unsubstituted cyclic olefins into cycloaddition products. When a potential of 1.25 V vs ferrocene was applied to a solution of cis-cyclooctene (COE) in dichioromethane/[NBu4][B(C6F5)(4)] containing a catalytic amount (4 mol %) of ReCp(CO)(3), 1, the olefin was converted to a diastereomeric mixture of the C-8-dimer tricyclohexadecane, with the major isomer having a cis-anti-cis geometry. Smaller cyclic olefins (C-5 to C-7) also formed cycloaddition products. The cyclization reactions require the electrogeneration of 1(+) as an electron-transfer mediator which triggers the one-electron oxidation of the otefin in spite of the fact that the potentials of the latter lie at considerably higher values. The very tow coulomb count required (ca. 0.1 F per olefin) for the conversion of olefin to product is consistent with a radical-chain mechanism. The electrochemical conversion of COE to cyclized products is complete in a few minutes, in contrast to the week-tong photochemical processes previously needed for preparation of the same cycloaddition products.