Nanostructured TiO2 has shown promise as a dielectric material for high energy density ceramic capacitors because of its high dielectric breakdown strength and dielectric constant. Strategies to increase the insulation resistance or to reduce the leakage current of TiO2 include doping with transition metal ions. It is shown that Mn doping followed by an appropriate thermal treatment increases the grain boundary resistivity significantly and lowers the dielectric loss. Electrical measurements along with electron paramagnetic resonance and scanning electron microscopy of Mn-doped nanoscopic TiO2 demonstrate that sintering at 900 degrees C leads to optimal electrical properties that are correlated with a non-uniform distribution of dopant ions, concentrated at the grain boundaries. Nanostructured TiO2 dielectrics with improved insulation resistance are promising for the development of higher energy density capacitors. (C) 2012 Elsevier B.V. All rights reserved.