Antimony selenide (Sb2Se3) has received considerable attention as a promising semiconductor material for both photovoltaic (PV) and PEC applications, owing to its low cost, suitable band gap (1.17 eV of direct band gap, and 1.03 eV of indirect band gap), low toxicity, high absorption coefficient (> 10 5 cm -1 ), and high carrier mobility (∼ 10 cm 2 V -1 s -1 ). The binary Sb2Se3 has only one stable thermodynamic orthorhombic phase, favoring the absence of secondary phases during synthesis. However, the anisotropic property of Sb2Se3 results in varying hole mobilities of 1.17, 0.69, and 2.59 cm 2 V -1 s -1 along the [100], [010], and [001] directions, respectively. Therefore, researchers have devoted significant efforts to optimizing crystal orientation and minimizing defects in Sb2Se3 films to enhance performance. Various methods for the preparation of Sb2Se3 have been explored in recent years, including thermal evaporation, closed-spaced sublimation, chemical bath deposition, sputtering, spin coating, and vapor transport deposition. Significant progress has been achieved using Sb2Se3 absorbers in PV cells and PEC water splitting since 2014. For example, a highly [001]oriented Sb2Se3 photocathode was successfully obtained by extending the selenization time within a sealed quartz tube, delivering a noteworthy photocurrent density of -20.5 mA cm -2 at 0 V versus reversible hydrogen electrode (VRHE). Post-annealing treatments were applied to the Sb2Se3 fabrication process to enhance crystallinity. Plus, post-selenization was used to address Se deficiency, mitigating bulk defects stemming from Se vacancies and antimony antisites. Zhao et al. achieved a record power conversion efficiency of 10.57% in Sb2Se3 solar cells by modulating deposition kinetics through the addition of selenourea during the chemical bath deposition process. Furthermore, the Moon group gained impressive progress in the Sb2Se3 photocathode through crystal and interface engineering within a short period, resulting in a substantial increase in photocurrent density from -2 mA cm -2 to -35 mA cm -2 at 0 VRHE, nearly reaching the theoretical maximum photocurrent density (∼ 40.9 mA cm -2 ). The Mai group found that controlling substrate temperature during sputtering allowed for the adjustment of the Sb2Se3 morphology and orientation. Inspired by these works, we investigated the impact of metallic Sb properties on the synthesis of Sb2Se3 films. Here, we report that the crystal orientation of metallic Sb can be controlled by manipulating the substrate temperature (25 o C and 75 o C) during thermal evaporation. For convenience, we designate the Sb thin films deposited at 25 o C and 75 o C as Sb-L and Sb-H, respectively. Notably, crystal planes with higher surface energy are preferentially exposed when the metallic Sb film is evaporated at higher temperatures. This selective exposure of specific crystal planes significantly influences the morphological evolution of Sb2Se3 during the selenization process. Accordingly, we denote the as-prepared Sb2Se3 thin films obtained from selenization of Sb-L and Sb-H films as Sb2Se3-L and Sb2Se3-H, respectively. The photocathode fabricated from Sb2Se3-H film, comprising thinner nanorods in the FTO/Au/Sb2Se3/TiO2/Pt configuration, achieves a remarkable photocurrent density of -22.1 mA cm -2 at 0 VRHE and an onset potential of 0.31 VRHE. In contrast, the Sb2Se3-L photocathode with thicker nanorods only exhibits -15.2 mA cm -2 at 0 VRHE and an onset potential of 0.21 VRHE. Moreover, the Sb2Se3-H photocathode demonstrates a lower dark current and a superior fill factor compared to the Sb2Se3-L photocathode. This straightforward enhancement in PEC performance of the Sb2Se3 photocathode, achieved through control of the metallic Sb films, represents a novel approach to synthesizing Sb2Se3 films.