Dielectric properties of titanium oxide ceramics are strongly influenced by the microstructural features and concentration of dopants and impurity ions. Electrical conductivity (via insulation resistance) of vanadium doped nanostructured titanium dioxide (TiO2) ceramics was measured as a function of donor concentration and temperature. In order to further clarify the effect of the dopants on the microstructural development and resultant dielectric properties of TiO2, electron paramagnetic resonance (EPR) spectroscopy was employed. Vanadium-doped TiO2 exhibited well-defined hyperfine splitting characteristics of the 51V nuclei indicating that the dopant ions are dispersed within the grains and not preferentially segregated at the grain boundaries.