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[Display omitted] • A functionalized material (CTAB-Pd/GAC) was synthesized as the catalyst. • CTAB could reduce the consumption of Pd for the catalyst. • Adsorption performance of catalyst was controlled by the amount of CTAB load. • Selective adsorption performance of the catalysts to 2,4-DCBA was enhanced. • The adsorption-desorption for 2,4-DCBA and BA was a dynamic process. The CTAB-Pd/GAC catalyst was obtained by functionalizing palladium/granular activated carbon (Pd/GAC) with cetyltrimethylammonium bromide (CTAB), which was used for the electrocatalytic reductive dechlorination of 2,4-dichlorobenzoic acid (2,4-DCBA). The degradation rate of 2,4-DCBA by 40 mg g−1 CTAB-Pd/GAC was 9.8 × 10−3 (min−1 g−1 Pd), which was 11 folds than that by Pd/GAC (0.9 × 10−3 min−1 g−1 Pd), and the value of q e, 2,4-DCBA / q e, BA was 2.33 as compared to 0.67 for Pd/GAC. The combined result of dechlorination and adsorption experiments suggested that the functionalization by CTAB would enhance the 2,4-DCBA concentration on the surface of CTAB-Pd/GAC, and accelerate the degradation rate. However, the removal efficiency of 2,4-DCBA would decrease when the CTAB load reached 80 mg g−1, due to the excessive adsorption capacity for dechlorinated product. Density functional theory (DFT) calculations also proved that CTAB would increase adsorption capacity of catalyst and selective adsorption behavior of 2,4-DCBA, which accelerated the degradation rate of 2,4-DCBA. [ABSTRACT FROM AUTHOR]