In this study, ethylenediaminetetraacetic acid (EDTA) modified hollow microporous organic nanospheres (EDTA-HMONs-BA) were prepared by a combination of one-pot hyper-crosslinking mediated self-assembly using polylactide-b-polystyrene (PLA-b-PS) diblock copolymer and benzylamine (BA) monomers as precursors and subsequent post-modification with EDTA. The obtained EDTA-HMONs-BA were characterized by FT-IR, TEM, TGA, solid state 13 C NMR, N 2 adsorption-desorption test et al. It revealed that the EDTA-HMONs-BA have a high specific surface area (226.86 m 2 g À 1 ), which exhibited excellent adsorption ability for Cu 2 + ions (236 mg g À 1 ) with adsorption characteristics of pseudo-second-order model and Langmuir isotherm equation. Moreover, the obtained adsorbent is of high stability after five consecutive cycles. Besides, EDTA-HMONs-BA also showed good adsorption capacities for hard acid metal ions (Cr 3 + ), soft acid metal ions (Ag + , Cd 2 + ), borderline acid metal ions (Cu 2 + , Ni 2 + , Zn 2 + ). The above results indicated that the EDTA-HMONs-BA can be considered as potential adsorbents for the removal of heavy-metal ions owing to the easily accessible adsorption sites and sufficiently good stability.