The dielectric properties of the system Li–Ti–O have been exploited in the frequency range 20 Hz–1 MHz in order to obtain permittivity data of materials having high-κ′ and low loss. Doping of titanium dioxide with lithium oxide acts as a strong promoter of the anatase to rutile phase transition and it may reduce the phase transition temperature (915 °C) by more than 100 °C, possibly due to induced oxygen concentration disorders in the ternary Li–Ti–O system. For TiO 2 :Li 2 O molar ratios of 98.92:1.08 and calcination temperature of 950 °C the resulting material exhibits high-κ′ and low-loss permittivity properties with lack of interfacial polarization effects. Its dielectric response is superior compared to pure (undoped) rutile as obtained by calcination at much higher temperatures (1180 °C).