Three coordination polymers were successfully constructed in this work by applying biligands and were distinctly characterized through single crystal X-ray diffraction. The compounds crystallized in acentric and centric space groups under the direction of coordination bonds and adopted 1-dimensional link and 2-dimensional layer structures, as well as different coordination geometries for metal atoms. All compounds exhibited good thermal stability and luminescence properties, and compound 2 exhibited a good second harmonic generation (SHG) response. The method used in this work offers a feasible approach to using biligand and changing metal salt to obtain the microstructures of coordination materials with specific properties.