A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17)center dot 3H(2)O that possesses both 1) optical transparency and 2) ion-exchangeability, the first example of such a material. An optically transparent Ru(bpy)(3)(2+)-K4Nb6O17 hybrid thin film, a potential photo-responsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV2+-K4Nb6O17 as a precursor.