The electrochemical reduction of chloromethyldimethylchlorosilane, affording 1,1,3,3-tetramethyl-1,3-disilacyclobutane, involves a dissociative electron transfer to the LUMO which contains the predominant contribution of the Si-Cl orbitals, and results in the C-CI bond cleavage. The reduction of trimethylchlorosilane occurs through the dissociative Si-Cl bond rupture. In the course of the reduction of chioromethyltrimethylsilane, the alpha-silicon stabilisation of the negative charge makes an individual anion radical to appear on the reaction coordinate.