Herein we report the synthesis, electrochemical and photophysical behaviors of TiO2/P-[Ru-pyr]2+ where a [Ru(bpy)3]2+ (bpy = 2,2’-bipyridine ) core bearing two pyrrole substituents on distinct bipyridines, and a phosphonic anchoring group are immobilized on TiO2 colloidal nanoparticles. Under visible light and in the presence of O2 as sacrificial electron scavenger, TiO2/[Ru-pyr]2+ was converted into a nanocomposite suprastructure TiO2/oligo(Ru-pyr) where [Ru(bpy)3]2+ units were linked together through pyrrole coupling reaction. The photo-induced charge separated state (e )TiO2/RuII-pyr+ was revealed by electron paramagnetic resonance (EPR) spectroscopy ((e )TiO2 signal). The oxidative coupling of pyrroles was ascertained by identifying the additional organic radical EPR signal with DFT calculations of pyrrole-derived oligomers, combined with X-ray photoelectron spectroscopy (XPS) results. TiO2/oligo(Ru-pyr) exhibited a higher rate of electron injection from [Ru(bpy)3]2+* to TiO¬2 than for colloidal nanoparticules without pyrrole denoted as TiO2/[Ru]2+. The composites were then electrophoretically deposited on a fluorine-doped tin oxide surface and tested as photoanodes. At a bias of 0.12 V. vs Ag/Ag+ 0.01 M, FTO/TiO2/oligo(Ru-pyr) in presence of tertiary amine as sacrificial electron donor, displayed a current density double that of FTO/TiO2/[Ru]2+ under similar condition. XPS confirmed the stability of [Ru(bpy)3]2+ photosensitizer core after the photopolymerization process, but a partial desorption was observed after the electrophoretic deposition.