Mesoporous materials have pores with diameters between 2 nm and 50 nm, the presence of which generally decreases the thermal conductivity of the material. By incorporating mesoporous structures into thermoelectric materials, the thermoelectric properties of these materials can be improved. Although TiO2 is an ordinary insulator, reduced TiO2 shows better electrical conductivity and is therefore a potential thermoelectric material. Furthermore, the addition of a dopant to TiO2 can improve its electrical conductivity. We hypothesized that, by doping ordered mesoporous TiO2 films with niobium, we would be able to minimize the thermal conductivity and maximize the electrical conductivity. To investigate the effects of Nb doping and a mesoporous structure on the thermoelectric characteristics of TiO2 films, Nb-doped mesoporous films were investigated using x-ray diffraction, ellipsometry, four-point probe measurements, and thermal conductivity analysis. We found that Nb doping of ordered mesoporous TiO2 films improved their thermoelectric properties.