The purpose of this work is to study the influence of the annealing temperature on the structural, morphological, compositional and optical properties of CuSbSe2 thin films electrodeposited in a single step. CuSbSe2 thin films were grown on fluorine-doped tin oxide (FTO)/glass substrates using the aqueous electrodeposition technique, then annealed in a tube furnace under nitrogen at temperatures spanning from 250 to 500 °C. The resulting films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis, Raman spectroscopy and UV-Vis spectrophotometer. The annealing temperature plays a fundamental role on the films structural properties; in the range 250–350 °C the formation of pure CuSbSe2 phase from electrodeposited binary selenides occurs. From 400 to 500 °C, CuSbSe2 undergoes a preferential phase orientation change, as well as the increasing formation of copper-rich phases such as Cu3SbSe3 and Cu3SbSe4 due to the partial decomposition of CuSbSe2 and to the antimony losses.