Reducing the mass transfer barrier for the diffusion of water and pollutants to Pd sites is an important measure to achieve efficient degradation of chlorinated organic compounds. Herein, a simple electroless deposition method for preparing a superhydrophilic nanosized Pd-loaded graphite felt/Ni electrode with the aid of the dispersibility of polyvinylpyrrolidone (PVP) and adhesiveness of polydopamine (PDA) is proposed. The GF/Ni/PDA/Pd-PVP electrode exhibited high electrocatalytic activity toward 2,4-dichlorophenoxyacetic acid (2,4-D) under the optimized conditions, namely degradation and dechlorination efficiencies of 90.5% and 88.53%, respectively, corresponding to 39% higher than that on the GF/Ni/Pd electrode. Experimental results revealed that PDA and PVP doping enhanced the hydrophilicity of the electrode, promoted the dispersibility of Pd nanoparticles (NPs), and the formation of Pd (111) and Ni (111) crystal facets. Compared to the electron-deficient PVP, the appropriate electron-donating ability of PDA promoted the formation of a suitable ratio of electro-deficient and electron-rich Pd, thus enhancing the production of Hads* and C-Cl scission. Moreover, theoretical calculation indicated that the doping of PDA and PVP optimized the adsorption energies of 2,4-D, Hads*, and the main dechlorination product PA, which was obtained via 4-electron transfer via Hads*. Therefore, this study provides a simple and feasible way to fabricate an efficient cathode for 2,4-D dechlorination.