A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17)(,)3H(2)O that possesses both (1) optical transparency and (2) ion-exchangeability under ambient conditions without calcination at high temperature. An optically transparent Ru(bpy)(3)(2+)-K4Nb6O17 hybrid thin film, a photoresponsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV2+-K4Nb6O17 as a precursor. The optically transparent Ru(bPY)(3)(2+) -K4Nb6O17 hybrid thin films have been characterized by X-ray diffraction, SEM, AFM, IR, and UV spectroscopies, as well as elemental analysis. The electrochemical behavior of the ITO/Ru(bpY)3(2+)-K4Nb6O17 hybrid thin film electrode was studied; it also exhibits swift photoresponse in the visible region.