Cu(Ⅱ)Coordination Supramolecule（Cu (C9H7NO)2）was synthesized in hydrothermal method, its single crystal structure being determined with X-ray diffraction. Structure analysis indicated that the hydrogen bonds in the crystal made the complex further connected to a supramolecule possessing an 1D infinite structure. Meanwhile, the IR spectrum, UV-Vis-NIR spectrum and the surface photovoltage spectrum (SPS) of the complex were measured and assigned exhibiting positive surface photovoltage responses in the range of 300～800 nm，meanwhile the absorption peaks in UV-Vis-NIR spectrum were in agreement with the responses in SPS. Field induced surface photovoltage spectrum (FISPS) show that the SPV responses' intensity of the complex increases linearly with the increase of the external positive field and reduces with the increase of the external negative field.