In this study, by controlling the temperatures of the source powder side and of the substrate side, α-HgI2 polycrystalline films are prepared by physical vapor deposition (PVD). The surface morphology and the degree of crystallinity of the as-grown α-HgI2 polycrystalline films are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), Respectively. For electrical properties, thermally stimulated current (TSC) measurements are performed to reveal the characters of deep-trapping levels. Furthermore, the temperature dependence of band gap deduced from photoconductivity (PC) spectra is measured, and the persistent photoconductivity (PPC) decay is studied.