We report the dielectric and electrical behavior of thermally evaporated lithium fluoride (LiF)-tungsten trioxide (WO3) (x wt% WO3-doped LiF; x = 0, 1, 3, 5, 7, 10) nano-composite thin films at room temperature over a wide range of frequencies from 0.1 Hz to 1 MHz. Among the various doping concentrations of WO3, the 5 wt% WO3-doped LiF nano-composite thin film reaches to the maximum dielectric constant similar to 25, compared with those of pure LiF similar to 9 thin film. The electrical studies of the films have been done by complex impedance spectroscopy and show the presence of grain and grain boundaries contribution in the films for all doping concentrations. The relaxation behavior in the nano-composite films has been observed in the dielectric curve at low frequencies which is superimposed by electrode polarization. The non-Debye type of relaxation in the films has been observed in the impedance and modulus curve. The peaks appearing at low frequencies for each doping concentration in loss tangent spectrum show the presence of relaxing dipoles in the films. An increment in the ac conductivity has been observed with doping concentration up to 5%. The ac conductivity curves obey the jump relaxation power law where an electrode polarization effect can be seen at low-frequency region.