Abstract The electrochemical behavior of cephalothin has been studied by a.c. and d.c. polarography, cyclic voltammetry, and coulometry in both aqueous and nonaqueous media in order to gain a greater understanding of the reaction pathways involved in cephalosporin reduction. The reductive allylic cleavage of the 3′-acetoxy function has been found to produce Δ3-deacetoxy and 3-exomethylene cephalothin compounds (geometric isomers) and stereochemical isomers of the 3′-exomethylene compound at the 4-position. The ratio of these compounds to one another is dependent on the experimental conditions used, with adsorption playing an important role. The reductive allylic cleavage of the S1−C2 bond is a competitive reaction pathway. Δ3-Deacetoxy cephalothin may undergo further reduction, depending on the electrolysis potential selected.