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.