Cu/Ni-bearing wastewater contamination has recently been a challenge for the environmental protection worldwide. Herein, a novel poly(2-acrylamide-pentanedihydroxamic acid) (PAPDA) resin containing –CONHOH and –COOH groups was prepared and applied to effectively remove Cu2+ and Ni2+ from heavy metal wastewater. The batch adsorption experiments revealed that the maximum adsorption capacities of PAPDA resin for Cu2+ and Ni2+ were 436.08 and 195.05 mg·g−1, respectively, which were 10.20 and 9.45 times higher than that of polyacrylic resin. Specifically, the adsorption kinetics and thermodynamics of PAPDA were respectively consistent with the pseudo-second-order kinetic model and the Langmuir isotherm model, indicating that the adsorption is a single-layer chemisorption process. Besides, the adsorption mechanism was investigated by SEM, XRD, FT-IR, XPS, DFT calculations, suggesting that the PAPDA resin possessing abundant active sites could effectively adsorb the heavy metal ions. Noticeably, the –CONHOH groups represented the strong affinity towards Cu2+ and Ni2+ by forming stable five-membered rings. In addition, column experiments were conducted to study the practical adsorption process of PAPDA resin to heavy metal ions. Overall, the results proved that the novel PAPDA resin as a green and highly efficient adsorbent has a promising potential for the treatment of heavy metals-containing wastewater. Display omitted •Novel acylamino dihydroxamic acid chelating resin (PAPDA) is designed and prepared.•PAPDA resin possessed multiple active sites that can be bound with the metal ions.•PAPDA resin achieved an excellent adsorption capacity for Cu2+and Ni2+.•PAPDA resin exhibited the faster adsorption rate for Cu2+ than that of Ni2+.•PAPDA resin presented effective stability and good regeneration property.