The electrochemical method for decomposition of halogenated organic compounds leads to a complete mineralization of organic halides. Considering the adiabatic electron transfer between the electrode (or catalyst) and organic polychlorides, the geometry optimizations at the UBP86/6-311++G** level of electronic structure theory of DDT, β-hexachlorocyclohexane, and heptachlor organic polychlorides as well as their positive (+1,+2) and negative (-1,-2) ions has been performed. The HOMO composition of these neutral molecules shows no contribution of the carbon-chlorine bonds atomic orbitals, while the LUMO of the calculated molecules includes a major contribution and antibonding character of the molecular orbitals from two or three carbon-chloride bonds of each calculated molecule. Consequently, the negative ions are the most sensitive structure during the geometry optimization, showing that the carbon-chloride bonds cleave during the electronic structure calculations. The investigation of the direct electrochemical reduction of organic polyhalides with vicinal halogens in an aprotic medium (DMF) shows that the corresponding olefin is formed according to a two-electron stoichiometry [1]. Two vicinal C-Cl bonds with significant antibonding contribution are present in the LUMO of the β-hexachlorocyclohexane neutral molecule. This leads to a concerted cleavage of two C-Cl bonds under the influence of the two-electron transfer. Indeed, the geometry optimization of the negative ions confirms the cleavage of two vicinal C-Cl bonds. The further geometry optimization of the molecular ions proves that the electrochemical dehalogenation of organic polychlorides must be sequentially leading to a fully dehalogenated benzene compound.