Environmental problems are usually related to the high levels of CO₂ in the atmosphere, where anthropogenic actions are the main sources of emissions. In this sense, one of the alternatives to decrease its concentration is the selective conversion of CO₂ into higher added value compounds. In the present work, three copper oxide samples with different morphologies were obtained by precipitation synthesis. The samples were deposited on ITO and 304 steel substrates by drop-casting technique to characterize the photoelectrochemical performance. For the physicochemical analysis of the samples the techniques of XRD, SEM, FTIR, diffuse reflectance spectroscopy and textural analysis (BJH) were used. The influence of NH₂OH∙HCl on octahedral, spherical and irregular obtained morphology was evaluated, as well as the effect of NaOH on particle size. For octahedral and spherical morphology, only Cu₂O were obtained, while for the sample with irregular morphology CuO (9.9%) was detected. The presence of CuO is due to the pH adjustment in the NH₂OH∙HCl solution, evidencing a modification of the microstructure and loss of its reducing power. Thus, the presence of Cu⁺ and Cu²⁺ ions contributed to the formation of irregular morphology. With the samples deposited in ITO the photoactivity was evaluated, in which all the electrodes presented an excellent performance with visible light (Egap ≈ 2.3 eV). To study the number of layers and photoelectrocatalytic performance, 304 stainless steel was used as substrate. Electrodes with 30 layers showed higher photocurrent and selectivity for CO₂ photoelectroreduction. The responses of the three electrodes were related to the specific area of the samples. The irregular morphology presented the largest area (25.04 m² g^-1), followed by the spherical one (15.20 m² g^-1) and with smaller the octahedral morphology (2.049 m² g^-1). The larger specific area allowed a better CO₂ adsorption besides the Cu₂O/CuO heterojunction which allowed a higher photocurrent (-3.0 mA cm^-2 at -0.8 V vs. Ag/AgCl). CO₂ photoelectroreduction products after 2 hours (-0.8 V application vs. Ag/AgCl) were evaluated by UV-Vis and HPLC spectroscopy. Using UV-vis spectroscopy, the presence of the band around 300 nm is associated with carbonyl grouping presented in the reduction products. By HPLC, such band was associated with formaldehyde, acetaldehyde and acetone. The octahedral morphology was more selective for formaldehyde formation, while the spherical one for acetaldehyde. For irregular morphology this selectivity was not observed resulting in similar intensity peaks.