A series of Pd/Fe2O3 nanohybrids with low metal content supported with Amberlite resin formate (Pd/Fe2O3@ARF) was prepared and characterized by FTIR, XRD, XPS, EELS, SEM–EDAX, and HRTEM. The coexistence of mainly crystalline Pd and Fe2O3 nanoparticles (NPs) of average size ∼4–5 nm in the resin matrix was confirmed. These nanohybrids were used for hydrodehalogenation of polyhaloaromatics using NaBH4 as a reducing agent in water. Notably, the composite Pd/Fe2O3@ARF-110 exhibits excellent catalytic performance in the hydrodehalogenation of different haloaromatics. High TOF (in comparison to other related heterogeneous catalysts), recyclability, and chemoselectivity between halide and C═C bond make this nanohybrid catalyst very attractive for the degradation of persistent organic pollutants originated from industries. The experimental observations and other analytical studies suggest that the enhanced catalytic activity could be due to strong interactions between Fe2O3 and Pd NPs that facilitate the cleavage of B–H bond and subsequent hydride generation.