Three rare heteromultinuclear complexes, ∞NiL(4,4′‐bipy)Pr (NO3)3·(CH3)2CHOH (1), {CuLSm (NO3)3}2(4,4′‐bipy)·CH3OH (2) and {CuL (CH3CH2OH)Eu (NO3)3 (3) with a symmetrical salamo‐like hexadentate ligand H2L have been synthesized, and characterized by FT‐IR, UV–vis and X‐ray crystallography. Complex 1 is a 1D coordination polymer constructed from heterobimetallic Ni(L)Pr (NO3)3 units which are connected by the exo‐dentate ligand 4,4′‐bipy bearing nitrogen‐donor atoms. Complex 2 is a heterotetranuclear dimer based on Cu(L)Sm (NO3)3 moieties which are linked through the exo‐dentate 4,4′‐bipy hasing nitrogen‐donor atoms. Complex 3 is a heterodinuclear structure, Cu (II) atom is five‐coordinate possessing a distorted square pyramidal geometry, and Eu (III) atom is a deca‐coordinate adopting a distorted bicapped square antiprism. In addition, fluorescence and antimicobial properties of the ligand H2L and its complexes 1–3 have also been discussed. Three rare heteromultinuclear complexes, ∞NiL(4,4′‐bipy)Pr (NO3)3·(CH3)2CHOH (1), {CuLSm (NO3)3}2(4,4′‐bipy)·CH3OH (2) and {CuL (CH3CH2OH)Eu (NO3)3 (3) with a symmetrical salamo‐like hexadentate ligand H2L have been synthesized, and characterized by FT‐IR, UV–vis and X‐ray crystallography. In addition, fluorescence and antimicobial properties of the ligand H2L and its complexes 1–3 have also been discussed.