Highly oriented polycrystalline Bi 2 S 3 thin films with crystallinities superior to those obtained in chemically deposited Bi 2 S 3 thin films were prepared by direct evaporation of bismuth sulfide precipitate. The XRD patterns of these films show preferential growth of bismuth and bismuthinite planes, and this growth could be correlated to substrate temperature and substrate type. For films deposited on glass substrates at room temperature, the XRD pattern shows an incipient growth of Bi 2 S 3 (bismuthinite) along the [020], [220], and [021] directions. At these angles, Bi planes also diffract and might be the major component of this alloy. XRD spectra of films deposited on bare glass in the substrate temperature range 150-300°C show that the film growth evolves from an oriented to a more random pattern. At a substrate temperature of 250°C, the crystallization of bismuth and bismuthinite is accelerated on glass substrates with a Cr coating and inhibited on glass substrates with a SnO 2 coating. The reflectance spectra of the films deposited at 250°C on uncoated and SnO 2 -coated glass substrates show that the crystallinity is dominated by Bi 2 S 3 , whereas in films deposited on a Cr grid Bi is a strong component. The optoelectronic properties of the deposited films indicate very conductive layered structures with E g values in the range 1.2-1.6 eV. Compared with the above, chemically deposited thin films were less crystalline and more stoichiometric, with a lower conductivity and higher optical band gap (1.5-2.0 eV). The possible application of these films in heterojunction and photoelectrochemical devices is suggested.