Li2S-2H(3)BO(3): xCoN(2)O(6 center dot)6H(2)O (x = 3, 4 and 5mol %) glass system was prepared. The microstructureand physical properties of glasses were characterized by X-ray diffraction (XRD), transmission electron microscopy(TEM), UV-Vis spectrophotometer and vibrating sample magnetometer (VSM). In order to measure the electrochemicalproperties of glasses, the cycling voltammograms (CVs) was employed where the highest specific capacitances of97.972 mV/s was obtained from x=5mol%. For structure-function of glasses, the S and Co oxidation states at S K-edgeand Co K-edge and local structure around Co ions were studied by X-ray absorption spectroscopy (XAS) including X-rayabsorption near edge structure (XANES) and extended X-ray absorption spectroscopy (EXAFS). It was found that, theS6+ oxidation state and mixing Co2+/3+ were revealed, respectively. Moreover, the Co K-edge EXAFS fitting wasexhibited co-existence of Co-A-O bond (tetrahedral coordination) and Co-B-O bond (octahedral coordination) in allfabricated glasses with a difference proportional site.