UV-vis light converts A-(DM)(2) (DM = 2,5-dimethyl-N,N'-dicyanoquionediimine; DMe-DCNQI) to several solids with metallic, semiconducting, or insulating conductivities depending on the irradiation conditions. Ag valence state in each photochemical product was determined by Ag L-3-edge XANES. The XANES result requires the correction of the redox mechanism to explain the photoinduced conductivity change of Ag(DM)(2) photoproducts.