Six cobalt complexes, Co(H2O)6·H2btec(1); {［Co2(HCOO)6］·CH3OH}n(2); {［Co(4,4’-bipy)2(H2O)4］·suc·4H2O}n(3); Co(NA)2(H2O)4(4); ［Co(mal)(4,4’-bipy)H2O］n(5) and ［Co(HCOO)4Co(H2O)4］n(6), were synthesized through hydrothermal method. UV-Vis absorption spectra and surface photovoltage spectra of the complexes were detected and the structures of the complexes were determined by single-crystal X-ray diffraction. There are positive responses in the range of 300-800 nm in the SPS. There are good corresponding relationships between response bands of SPS and absorption peaks of UV-Vis absorption spectra by the comparison. Comparing the SPS of six complexes, the valence, coordination mode and coordination micro-environment affect the position and the shape of the response bands.