Two nickel coordination complexes [Ni3 (btc)2 (H2O)14]·4H2O(1), [Ni2 (btec) (bipy)2 (H2O)6]·2H2O(2), (H3btc =1,3,5-benzenetricarboxylic acid, H4btec = 1,2,4,5-benzenetetra carboxylic acid, bipy =2, 2'-bipyridyl) were synthesized hydrothermally and characterized by single crystal X-ray diffraction (XRD), infrared (IR) and Ultravialet-Visible-Near Infrared (UV-Vis-NIR) spectra. Result indicate that complex (1) is a trinuclear complex bridged by btc groups and complex (2) is a binuclear complex connected by btec groups. The existence of hydrogen bonds allows complexes (1) and (2) to become coordination supramolecules with three dimensional (3D) and two dimensional (2D) infinite structures, respectively. Surface photovoltage spectrum(SPS) of these complexes exhibits positive surface photovoltage responses from300-800 nm. However, the intensity, position and shape of these response bands are obviously different. This distinction might be responsible for the structures and coordination environments of nickel ions in these complexes. By contrasting SPS with UV-Vis-NIR spectra we find that these response bands in SPS are consistent with absorption peaks in the UV-Vis-NIR spectra.