Heavy metal wastewater pollution has become an ecological challenge worldwide. This study reports the development of a novel poly (6-acryloylamino-N-hydroxyhexanamide) (PAHHA) resin for effective adsorption of heavy metal ions, including Cu2+, Pb2+ and Ni2+. The chelating resin was synthesized by the grafting reaction between 6-amino-N-hydroxyhexanamide and polyacrylic resin, thus containing the hydroxamate and acylamino groups. The batch adsorption experiments revealed that the PAHHA resin exhibited an excellent adsorption performance for Cu2+, Pb2+ and Ni2+. The maximum adsorption capacities of Cu2+, Pb2+ and Ni2+ were determined to be 238.59, 232.48 and 115.77 mg·g−1, respectively. Based on the adsorption kinetics, the pseudo-second-order kinetic model was noted to fit well for all metal ions. The metal ion concentration as a function of the equilibrium adsorption capacity fitted well with the Langmuir isotherm, thus indicating the single layer adsorption process. The adsorption mechanism was investigated by using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS) and adsorption isotherms. It was revealed that the PAHHA resin possessed multiple active sites, including –CONHOH, –CONH– and –COOH, which could strongly adsorb the metal ions. Specifically, the –CONHOH group displayed a high affinity by forming a stable five-membered ring with heavy metal ions. Overall, the developed resin exhibits advantages such as simple synthesis, inexpensive raw material and good recyclability, along with high adsorption ability, thus providing a new approach for efficiently treating wastewater contaminated with heavy metal ions.