Three 1,10-phenantroline zinc halide complexes were successfully synthesized under solvothermal method and structurally characterized by single-crystal X-ray diffraction analysis. The three title complexes Zn(1,10-phen)I ₂ (1), Zn(1,10-phen) ₂I ₂ (2) and Zn ₂(1,10-phen) ₂C ₂O ₄Br ₂ (3), crystallize in the triclinic space group P1¯(No.2) with different unit cell parameters, are isolated neutral molecules. The extra stretching force from another 1,10-phen ligand in 2 lead to the Zn−N bond lengths longer than the corresponding in 1. Meanwhile, the molecules of Zn(1,10-phen)I ₂ and Zn(1,10-phen) ₂I ₂ further connect each other via the π-π interactions between the adjacent phenanthrolines to form a pseudo-two-dimensional layer which parallel to b-axis. Their face-to-face distance of π-π stacking interactions between the adjoining 1,10-phen rings is 3.7264 Å and 3.4435 Å, respectively. The zinc bromide complex 3 contains C−H···O intramolecular and C−H···Br (2-D) interlayer hydrogen bonding, which contributed to the connection between the parallel zig-zag molecules. The distance of phenanthroline rings in intramolecular and interlayer is 2.6071 Å and 3.8125 Å. The luminescent emissions of free ligand 1,10-phen and its zinc halide complexes were measured in various solvents. These zinc halide complexes show the obvious luminescent phenomenon with grass-green, yellow-green and light yellow in Dimethyl sulfoxide (DMSO), respectively (the maximum emission wavelength is 530 nm, 539 nm and 496 nm). The maximum emission wavelength for 2 has a little red-shifted compared with 1. It can be concluded that the number of ligand and the electron density on coordinated Zn atoms influence the emission wavelength through charge transfer from ligand to the metal. The emission wavelengths of 3 are also slightly red-shifted compared with the free 1,10-phen ligand, which is attributed to the coordination effects of the 1,10-phen ligands to the Zn cations and [C ₂O ₄] ²⁻ group.