The study of electrochemical behavior of organic-inorganic nanocomposite materials remains a major challenge for application in energy storage devices. Here, new composite materials of chitosan and NiO nanoparticles have been fabricated. The NiO nanoparticles are well characterized by infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The electrical properties of the films are studied by impedance spectroscopy at different temperatures; and thereby permittivity, electric modulus and conductivity data are obtained. By studying the variations in permittivity and electric modulus spectra with respect to applied frequency signal and temperature, the ionic conductivity of the material is investigated. The Correlated Barrier Hopping model is employed to understand the conduction mechanism. An admirable conductivity of 1.4 x 10(-2) S cm(-1) is obtained for a nanocomposite with 4 wt% NiO content. The activation energies of the composite films decrease with increase in NiO content, from 16.5 to 4.8 kJ mol(-1).