The factors that control the successive reductive expulsion of chloride ions from aliphatic gem-polychlorides are investigated, taking as examples the electrochemical reduction of polychloromethanes and polychloroacetonitriles in N,N-dimethylformamide. At each elimination stage, the reaction involves, as a rate-determining step, the transfer of one electron concerted with the cleavage of the carbon-chloride bond. The second step is an immediate electron transfer to the ensuing radical, taking place at a potential more positive than the potential at which the first electron transfer occurs. The carbanion thus formed is sufficiently basic to be protonated by any trace weak acid present in the reaction medium. The three successive elimination steps require increasingly negative potentials. Application of the "sticky" dissociative electron transfer model allows one to quantitatively unravel the factors that control the energetics of the successive reductive expulsion of chloride ions. The-large potential gaps between each stage stem primarily from large differences in the dissociative standard potentials. They are also strongly affected by two cumulative intrinsic activation barrier factors, namely, the bond dissociation energy of the substrate that decreases with the number of chlorine atoms and the interaction between chloride ion and the radical that increases in the same direction. In the case of alpha,beta-polychloroethanes (Cl3C-CCl3, Cl2HC-CCl3, Cl2HC-CHCl2, ClH2C-CHCl2) too, the first step is a dissociative electron transfer with sizable ion-radical interactions in the product cluster. Likewise, a second electron transfer immediately leads to the carbanion, which however prefers to expel a second chloride ion, leading to the corresponding olefin, than to be protonated to the hydrogenolysis product. The ion-radical interaction in the product cluster plays a major role in the control of the reduction potential. The reduction of the alpha,beta-polychloroethenes (Cl2C=CCl2, ClHC=CCl2, ClHC=CHCl) follows a similar 2e(-)-2Cl(-) reaction sequence, leading then to the corresponding alkynes. However, unlike the polychloroethane case, the expulsion of the first chloride ion follows a stepwise electron transfer/bond cleavage mechanism. The reduction potential is thus essentially governed by the thermodynamics of the anion radical formation.