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Antimony selenide (Sb₂Se₃) has excellent directional optical and electronic behaviors due to its quasi‐1D nanoribbons structure. The photovoltaic performance of Sb₂Se₃solar cells largely depends on the orientation of the nanoribbons. It is desired to grow these Sb₂Se₃ribbons normal to the substrate to enhance photoexcited carrier transport. Therefore, it is necessary to develop a strategy for the vertical growth of Sb₂Se₃nanoribbons to achieve high‐efficiency solar cells. Since antimony sulfide (Sb₂S₃) and Sb₂Se₃are from the same space group (Pbnm) and have the same crystal structure, herein an ultrathin layer (≈20 nm) of Sb₂S₃has been used to assist the vertical growth of Sb₂Se₃nanoribbons to improve the overall efficiency of Sb₂Se₃solar cell. The Sb₂S₃thin layer deposited by the hydrothermal process helps the Sb₂Se₃ribbons grow normal to the substrate and increases the efficiency from 5.65% to 7.44% through the improvement of all solar cell parameters. This work is expected to open a new direction to tailor the Sb₂Se₃grain growth and further develop the Sb₂Se₃solar cell in the future.