This study proposes a green purification strategy in which mild decomplexation of Ni-EDTA into other Ni complexes facilitates the efficient removal and recovery of nickel through resin adsorption. Decomplexation of Ni-EDTA by boron/Fe2+/H2O2 (B/Fe2+/H2O2) followed by resins adsorption was conducted for Ni(II) removal in Ni-EDTA. The Ni(II) removal efficiency could only achieve 1.3 % and 6.2 % while Ni(II) coexisted with EDTA but more than 10 times of higher when Ni(II) coexisted with EDTA-relatives via the single adsorption of commercial heavy metal-affined resins (D001 and D463), which attributed to the increased binding energies of these Ni-EDTA’s degradation products complexes than Ni-EDTA based on density functional theory (DFT) calculation. In comparing to precipitation, the resin adsorption required much less mineralization of EDTA to have a better removal efficiency of Ni(II). B improved the efficiency of Ni-EDTA decompexation by accelerating the recycle of Fe3+/Fe2+. The EDTA (and TOC) removal enhanced from 48.7 % (4.7 %) to 94.7 % (11.9 %) by B/Fe2+/H2O2 process comparing to Fe2+/H2O2 process. With the high EDTA but low TOC removal efficiency after B/Fe2+/H2O2 treatment, Ni(II) removal efficiency via resins adsorption could maximum achieve 80.5 %, 2–3 times of that via regular precipitation method. In addition, B and resins exhibited good reusability in five cycles, and B/Fe2+/H2O2-resins process had excellent adaptability to different heavy metal complexes. B/Fe2+/H2O2-D463 system not only could reduce 78.4 % reagents cost compared with that of Fe2+/H2O2-precipitation process, but also could save much cost than other processes. The results provide new insights for the cost-effective treatment of EDTA-complexed heavy metal wastewater.