Current-reversal chronopotentiometry was used to measure the rates of decomposition of tertiary alkyl radical anions. Radical ions studied were chosen to yield both constrained and unconstrained products (e.g., 1-nitroadamantylvs.t-nitrobutyl) in an effort to illuminate the effect that such structural differences might have upon the decay rates. Temperature studies were performed to yield thermodynamic details; supporting electrolyte concentration changes and three solvents were employed to explore ion pairing effects.