Three Co-M (M = Cd, Zn, Co) coordination polymers, [CoCd (mal)(2) (H2O)(4)](n) (1), [CoZn (mal)(2) (H2O)(4)](n) (2) and [Co-2 (mal)(2) (H2O)(4)](n) (3) (mal = malonate), were synthesized by hydrothermal method and structurally characterized by X-ray single crystal diffraction. The structure analysis shows that the three coordination polymers all possess 2D layer structure constructed by mal anion bridging Co(11) and M(II) ions. The layers are further linked by the hydrogen bonds, producing 3D network structure. The measurement and analysis of surface photovoltage spectroscopy (SPS) and UV-Vis spectra indicate that the three polymers exhibit positive surface photovoltage responses in the range of 300-600 nm, moreover, the SPS also present a consistency with UV-Vis spectra.