CuGaS₂-based photocatalysts were studied for CO₂ reduction under photoelectrocatalysis (PEC) technique. The CuGaS₂ was modified with small amounts of In or Bi to analyze the interference of these metals in the products generation. The doped and non-doped CuGaS₂ were deposited by spray coating on Mo using inks comprised by the respective salts of each cations, and thiourea as the source of sulfur. A CdS and TiO₂ thin films were deposited by a chemical bath deposition method on the spray-coated CuGaS₂ films. The photoelectrodes were characterized by XRD, Raman, SEM, EDS, Diffuse Reflectance and XPS. The photoelectrocatalytic reductions of CO₂ were performed in a one-compartment glass reactor (50 mL) equipped with quartz window, at 20 ^oC, and three electrodes: Pt foil (counter electrode), Ag/AgCl (KCl sat) (reference electrode), and the semiconductors as working electrode, with 0.1 mol L^-1 Na₂SO₄ saturated with CO₂, irradiated by a 150 W commercial solar simulator lamp (Newport 66902) and submitted to a controlled potential (potentiostat/galvanostat - Autolab PGSTAT 302, Metrohm). Aliquots of the solution were evaluated by CG-FID[1]. The CuGaS₂ and Cu(In,Ga)S₂ electrodes presented a more stable photocurrent along the time analyzed, indicating a better stability of the material compared to Cu(Ga,Bi)S₂ electrode. The CO₂ reduction was performed under -0.7 V and light incidence (one sun) with the three electrodes. Comparing the amount of methanol (the main product for all the electrodes), it was higher employing Cu(In,Ga)S₂ electrode than under CuGaS₂ and Cu(Ga,Bi)S₂. However, the formation of other products that require a higher number of electrons and protons (ethanol and acetone) was higher under the CuGaS₂ catalyst. In addition, the stability and, consequently, repeatability of the products concentration formed using CuGaS₂ for consecutive reactions of CO₂ reduction is better than the observed for the catalysts modified with In or Bi. In fact, the Bi presence did not improve the CuGaS₂ activity for CO₂ reduction. After 240 min of CO₂ reduction using CuGaS₂ semiconductor under -0.7 V and light incidence (one sun) were quantified 1.30 mmol L^-1 methanol, 0.45 mmol L^-1 ethanol and 0.25 mmol L^-1 acetone. So, despite the improvement for methanol production obtained in the first 4h of reaction with the addition of In in the semiconductor surface, the results obtained under CuGaS₂ electrode without further modification showed to be superior for CO₂ reduction using PEC technique.