A new trinuclear nickel(II) complex, {NiL(EtOH)(μ-OAc)} 2 Ni·2CH 3 CH 2 OH were synthesized via the reaction of a salamo-type ligand H 2 L with nickel(II) acetate tetrahydrate by wet-chemical method. The complex was characterized by single crystal X-ray diffraction and various spectroscopic methods. Crystallographic data showed that all the nickel(II) atoms are located in N,O-donor cavities possess distorted octahedral geometries. Through intermolecular interactions, the complex finally forms a three-dimensional supramolecular structure. Remarkable, there is an obvious lone pair–π interaction between the complex units. Intermolecular interactions are carefully discussed by Hirshfeld surfaces analyses. Meanwhile, fluorescence properties are performed in ethanol.