Chirality effects have been observed in the intercalation, spectroscopic and photoelectrochemical behavior when enantiomeric and racemic [Ru(phen)(3)](2+) complexes were intercalated in the interlayer spaces of K4Nb6O17. The results were interpreted in terms of a [Nb6O17](4-) -chelate and chelate-chelate interactions. The faster luminescence decay and higher photocurrent of the enantiomeric [Ru(phen)(3)](2+) -K4Nb6O17 Compounds than the racemic ones suggest that the emission of adsorbed [Ru(phen)(3)](2+) ions was not only quenched by adsorbed complexes (or concentration quenching) but also by the semiconductive host lattices.