In this work the electrochemical degradation of polychlorinated compounds using Co(dmgH)2Cl(py), Co(dpgH)2Cl(py), Co(chgH)2Cl(py) and Co(dbegH)2Cl(py) (where dmgH is dimethylglyoximato, dpgH is diphenylglyoximato, chgH is 1,2-cyclohexanedionedioximato and dbegH is di(4-methylbenzoate)glyoximato) is described. The degradation was studied using cyclic voltammetry by monitoring current changes in the zone near to the Co(II/I) half wave potential as the concentration of the organochloride in the electrochemical cell is increased. Hexachloroethane (HCA) was used as organohalide substrate, while gamma-hexachlorocyclohexane (lindane), 1,2-dichloroethane, and 1,1,1-trichloroethane were used for comparative studies.  The major dechlorination product of HCA, detected through head space GC-MS experiments after bulk electrolysis, was tetrachlorethylene. The rate constants of the dechlorination processes were estimated using the foot-of-the-wave analysis (FOWA), the values obtained were 1.10×105, 2.59×104, 4.91×104   and 1.83×104 for Co(dmgH)2Cl(py), Co(dpgH)2Cl(py), Co(chgH)2Cl(py)  and Co(dpegH)2Cl(py) respectively.