In this paper, we investigated the effect of Zn1-yMgyO/ZnO1-xSx double buffer layers on the antimony selenide (Sb2Se3) solar cells performance. Our results show that the magnesium and sulfur concentrations in proposed double buffer layers have a significant effect on the band alignment optimization at the junctions. The flexibility with Zn1-yMgyO/ZnO1-xSx double buffer layers ranging from 0 to 25% magnesium and 10%–70% sulfur allows an optimal conduction band offset (CBO) for Sb2Se3 solar cells. An improved open-circuit voltage (Voc) was observed in the Sb2Se3 solar cell with Zn0.93Mg0.07O/ZnO0.4S0.6 proposed double buffer layers due to appropriate CBO values at the junction interfaces. The short-circuit current density (Jsc) values increased as the sulfur concentration in the ZnO1-xSx buffer layer increased from 0 to 0.7 (x value), which could be related to the increase in the optical band gap of the ZnO1-xSx layer. The results demonstrated that under small positive offset conditions (spike-like), the carrier recombination rate at the interface is reduced, and consequently, the Sb2Se3 solar cell performance is improved. A Sb2Se3 solar cell with the optimum CBO amount (+0.3 eV) represented a conversion efficiency of 15.46%, which exhibited a 68% enhancement in comparison to the traditional CdS/Sb2Se3 solar cell.