Bi:ZnSe films at different concentrations (0, 5, 10, and 15%) were made by the laser deposition technique. The scanning electron microscopy and Uv–visible spectroscopy were used to investigate the surface topography and optical properties of the prepared films, respectively. The calculated energy gap was (3.0, 2.6, 3.2, and 3.1 eV) due to differences in lattice parameters. Moreover, the electrical characteristics reveal enhanced dark current with all samples probably due to the essential property of p-type doped ZnSe Nano-composition. The density, refractive index, permittivity, and reflection loss were also studied versus Bi-dopant. The structural characteristics of the coated films have been tested by an X-ray diffractometer. In addition, the interstitial or substitutional Zn ion by Bi ion in the lattice was also explained in this paper.