In this study, we explored the effect of either Nb or Sc doping at a concentration range of 0.0–1.0 at.% on the physical–chemical and photoelectrochemical behavior of TiO2 anatase electrodes. This behavior was characterized by work function, flat band potential, donor density, spectral dependence of photocurrent and stationary photocurrent measurements. All experimental results are interpreted in terms of the formation of the shallow delocalized polaron states in the case of Nb doping and deep acceptor states induced by Sc doping on TiO2 anatase.