Bismuth selenide (Bi2Se3) is a semiconductor of great interest for application in energy conversion systems. In this work, the impact of electrolyte temperature on the morphology, crystalline structure, and optical properties of electrodeposited Bi2Se3 films was studied on several conductive substrates. The layers were grown by potentiostatic deposition with electrolytes at 25 °C (RT) and 60 °C on Cr, ITO, and Au substrates. The SEM analyses show that compact and smooth films are obtained when the electrolyte is heated, whereas rough layers are formed at RT depositions. The XRD measurements indicated that the growth depends on substrates and electrolyte temperature, with the samples grown over Au demonstrating a higher crystalline quality. TEM analyses revealed nanostructured regions with monocrystalline SAED patterns are formed when the films are grown on Au at RT, while for the same substrate the depositions with electrolyte at 60 °C result in regions with a polycrystalline nature. The optical characteristics revealed bandgap values close to 1.50 eV that are obtained by adjusting the electrodeposition conditions.