The electrical properties of cement–polyvinyl alcohol were studied using the impedance measuring technique. The study has been carried out under different temperatures and frequencies. Some electrical quantities such as AC conductivity, dielectric constant, activation energy, and relaxation time of the conduction process were determined from collected impedance data, at a frequency range from 20 kHz to 1 MHz and temperatures of 30–105°C. It was found that the measured electrical quantities have frequency and temperature dependence. The dielectric constant and dielectric loss increase with increasing temperature and decrease with the applied frequency. The AC conductivity increases with increasing temperature and frequency. The calculated values of the activation energy and relaxation time vary with temperature and frequency. The observed enhancement in the electrical conductivity with increasing temperature may be due to electron hopping between the intrinsic localized states in composite composition. The increase in the dielectric constant with temperature is attributed to space charge, ions, and metallic inclusions existing in the cement structure.