The selective dechlorination of various chloroaromatics in water-MeOH medium containing trifluoroacetic acid and tetraalkylammonium salts was successfully performed over Pd-loaded carbon felt cathode at room temperature. The reactivities of 2,4-dichlorophenyl derivatives varied in the order: 2,4-dichlorotoluene < 2,4-dichlorophenol ≤ 2,4-dichloroanisole ≤ 2,4-dichlorobenzoic acid < 2,4-dichlorophenoxyacetic acid < 2,4-
dichlorophenethyl alcohol. For 2,4-dihaloanisoles, the ease of reductive cleavage of C--X (X=halogen) bond was as follows: F
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Cl < Br. For monochlorobiphenyls, the dechlorination and product recovery efficiencies were remarkably affected by tetraalkylammonium cations of different size. The reaction scheme for the selective electrocatalytic dehalogenation of haloaromatics over Pd-loaded felt cathode was proposed.