An independent self-assembling heterobimetallic [Ni(II)–Eu(III)] salamo-like coordination polymer, $$^1_\infty$$ [Ni(L)Eu(NO3)3(4,4′-bipy)], is synthesized by the one-pot reaction of a symmetrical salamo-like hexadentate ligand (H2L = 6,6′-dimethoxy-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol), Ni(OAc)2·4H2O, Eu(NO3)3·6H2O, and 4,4′-bipy. The coordination polymer is obtained by the reaction in the 1:1:1:1 ratio and characterized by elemental analyses, IR and UV-Vis absorption spectra, and single crystal X-ray diffraction. The newly synthesized polymer is constructed from heterobimetallic [Ni(II)(L)Eu(III)] units connected by the 4,4′-bipy exodentate ligand bearing N donor atoms. Meanwhile, the hydrogen bonding, π⋯π stacking and C–H⋯π interactions play an important role in the structure of the coordination polymer. In terms of the antibacterial activity, the polymer dissolved in DMF has a good antibacterial effect on Staphylococcus aureus.