Different spectroscopic and photoelectrochemical behaviors were observed when racemic and enantiomeric[Ru(bpy)(3)](2+) complexes were intercalated in the interlayer of K4Nb6O17, even for the same intercalation amount. The results are interpreted in terms of the stronger interaction between racemic [Ru(bpy)(3)](2-) molecules in the interlayer spaces of K4Nb6O17,. The faster emission decay and lower photocurrent of the racemic [Ru(bpy)(3)](2-)-K4Nb6O17 compound compared to the enantiomeric ones suggest that stronger concentration quenching exists between the racemic [Ru(bpy)(3)](2-) ions in the interlayer of 1,K4Nb6O17,. Combining the spectroscopic and photoelectrochernical results, the racemic [Ru(bpy)(3)](2-) ions are considered to intercalate more densely than the enantiomeric [Ru(bpy)(3)](2+) ions in the interlayer of K4Nb6O17, even for the same intercalation amount. Two cationic dyes were also directly intercalated into K4Nb6O17. The spectroscopic and photoelectro chemical behaviors of the dye-K(4)Nb(6)O(17)compounds were investigated.