This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO2) films from the decomposition of Ti(OEt)4 with dopant quantities of Nb(OEt)5 by aerosol -assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n-type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO2 films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 1021 cm−3 with a mobility of 2 cm2 V–1 s–1 . The corresponding sheet resistance was as low as 6.5 Ω sq–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO2 films synthesized by vapour deposition. The doped films were also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO2 lattice. Computational methods also confirmed experimental results of both delocalized (Ti4+) and localized polaronic states (Ti3+) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO2 combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.