Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(HO)](1) and [Cd(μ-Hcpia)(μ-Hbiim)(μ-Hbiim)(HO)](2), have been constructed hydrothermally using Hcbia(Hcbia = 5-(4’-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4’-bipyridine), Hbiim(Hbiim = 2,2’-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the Hcpia(Hcpia = 5-(4’-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in Hcbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.