PIOS (penning ionization optical spectroscopy) method was used to investigate structure of ionized CS2. Emission of CS+ (A2∏i→X2∑+) 13-2 and 14-3 bands in CS2/He and OS2/Ne penning ionization flowing afterglow was observed in the wavelength region between 470-490nm when high discharge current was used. Experimental result showed that the above emission was preferential in CS2/Ne system. Secondary collision was assumed as the reason of the emerging of these emisson.