Electrocatalytic　hydrogenolysis　(ECH)　of　chlorophenols　in　aqueous　solution　was　achieved　on　a　novel　electrode.　Polymeric　pyrrole　(PPy)　film　and　surfactant　sodium　dodecylbenzene　sulfonate　(SDBS)　were　used　for　preparation　of　Pd-Ni　bimetallic　cathode,　which　was　marked　as　Pd58Ni42(SDBS)/PPy/Ti　cathode　due　to　Pd　and　Ni　loading　amounts.　High　electrocatalytic　activity　could　be　achieved,　by　the　synergistic　effect　of　PPy　and　SDBS,　meanwhile,　the　loading　of　Pd　could　be　decreased　by　0.35　mg/cm(2).　Effective　dechlorination　processes　of　pentachlorophenol　(PCP)　and　2,4-dichlorophenol　(2,4-DCP)　were　investigated.　Complete　decomposition　of　PCP　could　be　achieved　under　the　conditions　of　current　of　5　mA,　initial　pH　in　cathode　compartment　of　2.0　and　dechlorination　time　of　90　min.　Complete　dechlorination　of　2,4-DCP　could　be　achieved　under　current　of　5　mA,　initial　pH　of　1.7　and　dechlorination　time　of　90　min.　Pathways　were　inferred　according　to　instantaneous　molar　concentration　of　the　intermediate　products.　The　formation　of　PPy　film　improved　the　stability　of　Pd58Ni42(SDBS)/PPy/Ti　cathode.　The　electrode　exhibited　promising　dechlorination　potential　with　high　electrocatalytic　activity,　good　stability　and　low　cost.　(C)　2013　Elsevier　By.　All　rights　reserved.