Transparent conductive oxides form an important group of materials that combine high conductivity with high transparency. In this context, the authors designed an atomic layer deposition process for Nb-doped TiO2. The presented process enables accurate control over both the position and concentration of the Nb dopants. The as-deposited films become crystalline (brookite) and low resistive (4.3 × 10−3 Ω cm) upon a postdeposition anneal with temperatures as low as 300 °C. Variations in annealing ambient and temperature yielded resistivity changes over four orders of magnitude and significant changes in the sub-bandgap absorption of light. Next to doping, annealing is therefore shown to be a powerful tool in controlling electrical and optical properties of TiO2:Nb.