Results pertaining to the direct and indirect electrochemistry of 5, 7-di-tert-butylspiro[2.5]octa-4, 7-dien-6-one (1a), 1-methyl-5, 7-di-tert-butylspiro[2.5]octa-4, 7-dien-6-one (1b), and 1, 1,-dimethyl-5, 7-di-tert-butylspiro[2.5]octa-4, 7-dien-6-one (1c) are reported. Product analyses reveal that reduction of all these substrates leads to cyclopropane ring-opened products; ring opening occurs with modest selectivity leading to the more substituted (stable) distonic radical anion. The direct electrochemistry of these compounds is characterized by rate limiting electron transfer (with alpha approximate to 0.5), suggesting that while ring opening is extremely rapid, the radical anions do have a discrete lifetime (i.e., electron transfer and ring opening are not concerted). Utilizing homogeneous redox catalysis, rate constants for electron transfer between la, Ib, and Ic and a series of aromatic radical anions were measured; reduction potentials and reorganization energies were derived from these rate constants by using Marcus theory.