Sb2Se3 is an emerging material among alternative light absorbers for photovoltaic applications. Unlike typical chalcogenides, Sb2Se3 is particularly appealing due to its single stable crystal phase, layered structure with loose binding of no dangling bonds. Nevertheless, a cost-effective electrochemical approach for the synthesis of Sb2Se3 compounds has not been identified, and the Sb2Se3 film with the most favorable [001] preferred orientation has only just been developed. In this study, Sb-rich precursors were prepared electrochemically at - 950 mV (vs. Ag/ AgCl), and homogeneous Sb2Se3 thin films were produced using a pre-thermal treatment process prior to the typical selenization process with additional Se coating. This novel procedure notably suppresses potential Sb dissolution into liquid Se due to the formation of polycrystalline Sb-related crystals. As a result, the Sb-rich precursor was successfully transformed into Sb2Se3 thin films with an enhanced perpendicular orientation of the [001] direction. Unfortunately, a high density of voids was produced in the precursor film with two distinguishable layers, and their size increased after selenization. The voids were formed through evolution of H2Se gas after the initial electrochemical reaction. The resulting photovoltaic cells demonstrated an energy conversion efficiency of 1.8% in a substrate structure consisting of Mo/Sb2Se3/CdS/ZnO/ITO.