Protective overlayers for light absorbers in photoelectrochemical water-splitting devices have gained considerable attention in recent years. They stabilize light absorbers which would normally be prone to chemical side reactions leading to degradation of the absorber. Atomic layer deposition (ALD) enables conformal and reproducible ultrathin protective layer growth even on highly structured substrates. One of the most widely investigated protective layers is amorphous TiO2, deposited by ALD at a relatively low temperature (120–150 °C). We have deposited protective layers from tetrakis(dimethylamido)titanium(IV) at two different temperatures and investigated their chemical composition as well as optical and electrochemical properties. Our main findings reveal a change in the flat band potential with thickness, reaching a stable value of about −50 to −100 mV versus reversible hydrogen electrode for films >30 nm, with doping densities of ∼1020 cm3. Practical thicknesses to achieve pinhole-free films are evaluated and discussed.