The effect of copper addition in the microstructure of sol-gel titanium oxide (TiO2) supported on anodic aluminum oxide (AAO) membranes is reported. Two deposition methods based on immersion and flow techniques were used for the coating of the porous AAO membrane. Copper-free membranes were studied as a function of different ratios of H+/Ti, H2O/Ti, selecting the most appropriate for the sensitization with copper. For copper-doped TiO2 arrays, the presence of copper causes the reduction of grain size and enhances titania deposition inside the AAO pores, although no clear tendency with copper content was found. The formation of copper-doped titania nanotubes was validated after dissolving the AAO membranes, finding a deposition-dependent stability in the Cu-doped materials. Titania and Cu-doped titania nanotubes analyzed as colloidal solutions show band gaps substantially shifted to the red in comparison to the direct band gap of near-spherical colloidal materials. These arrays are important for photocatalysis and for the development of third generation photovoltaic devices.