High permittivity (Li, Fe)-doped NiO (LFNO) ceramics are prepared by a simple PVA sol-gel route and their dielectric properties are investigated as functions of temperature and frequency. It is found that the concentrations of Li and Fe have strong influences on the microstructure and dielectric properties of the LFNO ceramics. Two thermally activated dielectric relaxations are observed in the Li0.05Fe0.10Ni0.85O ceramic sample with the activation energies of 0.448 and 0.574 eV for the high- and low-frequency relaxations, respectively. By using a complex impedance analysis, it is believed that the high-frequency relaxation is closely related to the transport properties inside the grains, and the low-frequency relaxation might be ascribed to the interfacial polarization at the interface layers of grain boundaries and/or NiFe2O4 secondary phase layers. (C) 2010 Elsevier B.V. All rights reserved.