Tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3)](2+))-fluortetrasilicic mica-poly(vinylpyrrolidone) intercalation compounds were prepared by the intercalation of poly(vinylpyrrolidone) into the presynthesized [Ru(bpy)(3)](2+)-fluortetrasilicic mica intercalation compounds. The formation of the intercalation compounds was confirmed by the expansion of the interlayer space as well as the spectroscopic observations. Intercalation compounds with variable chemical compositions have been prepared, and the effect of the distribution of the intercalated [Ru(bpy)(3)](2+) on the luminescence has been discussed. The luminescence probe can be utilized for the study of clay-polymer interactions.