Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H₂O)₂]_n (1) and [Cd₃(μ₃-Hcpia)₂(μ- Hbiim)₂(μ-H₂biim)(H₂O)₂]_n (2), have been constructed hydrothermally using H₂cbia (H₂cbia = 5-(4΄-cyano- benzoxy)isophthalic acid), bipy (bipy = 4,4΄-bipyridine), H₂biim (H₂biim = 2,2΄-biimidazole), and manganese or cadmium chlorides at 160 °C. Interestingly, the H₃cpia (H₃cpia = 5-(4΄-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H₂cbia. 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 P. 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 3,4,4T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.