At vitreous carbon electrodes in dimethylformamide which contains tetramethylammonium perchlorate, cyclic voltammograms for 1-iododecane, 1-bromodecane, and 2-bromooctane consist of one irreversible reduction wave signaling formation of the alkyl carbanion, whereas voltammograms for 2-iodooctane, t-butyl bromide, and t-butyl iodide reveal stepwise generation of the alkyl radical and carbanion. Large-scale electrolysis of 1-iododecane at reticulated vitreous carbon yields decane, eicosane, 1-decene, and 1-decanol; the first two compounds arise, respectively, from reaction of decyl carbanions with a proton donor and with unreduced alkyl iodide, whereas the last two species are produced via chemical attack of hydroxide ion on 1-iododecane. Reduction of 1-bromodecane results in production of decane, 1-decene, and 1-decanol, but little or no eicosane is seen. Electrolysis of 2-bromooctane gives octane, 1-octene, 2-octene, 2-octanol, and 7,8-dimethyltetradecane, the last species probably being formed by coupling of 2-octyl radicals; the other compounds are derived from the 2-octyl carbanion. Although products obtained upon reduction of 2-iodooctane are identical with those from 2-bromooctane, both radicals and carbanions (the relative amounts of which are potential dependent) are involved in the formation of products from the secondary alkyl iodide. A combination of reactions involving t-butyl radicals and t-butyl carbanions is responsible for production of isobutane, isobutylene, and 2,2,3,3-tetramethylbutane during electrolyses of t-butyl bromide.