In this present study, the thin film of bismuth and antimony is coated by thermal evaporation system equipped with the inbuilt ultra high vacuum system. XRD analysis confirmed the rhombohedral structure of Bismuth and Antimony on the prepared film. The surface roughness and physical appearance is analyzed by Atomic force microscopy. The results of Raman Spectroscopy show the wave functions and the spectrum of electrons. The preparation technique and conditions strongly influence the crystalline structure and the phase composition of bismuth and antimony thin films. The electrical and optical properties for the prepared film are analyzed. The results show a great interest and promising applications in Photovoltaic devices. © 2016 Elsevier Ltd. All rights reserved.