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In this work, we present a novel resistless patterning technique on hydrogen-terminated Si (100) using EUV-induced surface reaction. We has successfully demonstrated a direct Si pattern transfer of half-pitch 75 nm Si gratings using the EUV resistless patterning technique. The EUV-induced surface reactions could achieve direct patterning on functionalized Si surface and potentially overcome the resolution limitations of conventional photoresists in the semiconductor industry. Moreover, this approach can be used for better understanding of EUV exposure mechanisms by preparing simple molecular systems and studying the EUV-induced reactions.