In this article we study the anchoring of cis-[Ru(bpyC(4)pyr)(CO)(2)(CH3CN)(2)](2+), cis-[Ru(bpy)(2)(CO)(2)](2+) and cis-[Ru(bpyac)(CO)(2)Cl-2], onto nanoporous TiO2 employing electropolymerization, electrostatic interaction and chemical bonding. Also, the [Re(bpyac)(CO)(3)Cl] rhenium(I) complex for chemical anchorage was analyzed. The characterization of TiO2/Ru(II) and TiO2/Re(I) nanocomposite films was performed by field emission scanning electron microscopy (FESEM), electron dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. In addition, for the more stable nanocomposites obtained, the catalytic properties (solar energy conversion and CO2 reduction) were evaluated. The efficiency improvement in redox process derived from the (photo)electrochemical evidence indicates that modified nanoporous TiO2 structures enhance the rate of charge transfer reactions. (C) 2018 Elsevier B.V. All rights reserved.