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Silicon photoepitaxy excited by synchrotron radiation (SR) has been observed for the first time. The epitaxial growth is observed even at lower than a 400 °C substrate temperature. The surface of the as‐grown film exhibits a 2×1 reconstruction reflection high‐energy electron diffraction pattern, indicating two‐dimensional growth. At lower than 600 °C, the SR‐irradiation growth rate is larger than that of thermal growth. This result suggests that SR irradiation enhances the dynamic surface reactions, such as desorption of hydrogen and surface migration of adsorbed species.