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Two new zinc(II) complexes, [Zn2(PBM)2(terephthalate)(formate)2] (1) and {[Zn(PBM)(fumarate)]∙H2O}n (2), were synthesized using 1,3-bis(1H-benzo[d]imidazol-2-yl)propane (PBM) and two different dicarboxylic acids under solvothermal conditions. Complexes 1 and 2 have been characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis. The structural analysis showed that 1 was a binuclear structure and then formed a 3D supramolecular network structure through hydrogen bond and π-π conjugation, while 2 was a one-dimensional coordination polymer. In 1 and 2, the zinc ions were four-coordinate with an N2O2 donor set and a slightly distorted tetrahedral geometry. The solid-state fluorescence properties indicate that the fluorescence peaks belong to the π*-π transition of the ligand PBM, which has a significant red shift and enhancement with the order being 1 > 2 > PBM. The stronger fluorescence of the complexes than the ligand is due to the immobilization of the ligand through coordination, which reduces the energy loss of thermal vibration. The π∙∙∙π conjugation in 1 results in a stronger fluorescence of 1 than 2. Therefore, coordination and π∙∙∙π conjugation will affect the fluorescence of complexes. [ABSTRACT FROM AUTHOR]