The dielectric behavior of two kinds of Li and Ti co-doped NiO (LTNO)/polyvinylidene fluoride (PVDF) composite was studied at various different frequencies and temperatures. The effective dielectric constant of the percolative composite at 100 Hz is very high, i.e., epsilon(eff) approximate to 600, which is 60 times higher than that of the PVDF. The results also show that there is a remarkable difference in the dielectric constant of the composites with different LTNO fillers. Boundary layer capacitor effect and percolation theory can be used to explain the experimental results. (C) 2003 Elsevier B.V. All rights reserved.