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Here we report an unprecedented nickel\u2010catalyzed 1,2\u2010arylalkenylation of unactivated alkenyl alcohols using alkenyl boronates and aryl iodides. This method uniquely leverages the native hydroxyl group as an intrinsic directing handle, eliminating the need for pre\u2010installed auxiliaries and streamlining the synthesis of structurally diverse alkenol derivatives. The reaction proceeds under mild conditions with broad functional group tolerance and excellent regioselectivity, enabling efficient construction of valuable building blocks. Mechanistic studies, supported by DFT calculations, reveal a Ni(0)\/Ni(I)\/Ni(II) catalytic cycle probably involving aryl radical intermediates. By exploiting alcohols as directing groups, this work expands the scope of alkene dicarbofunctionalization and provides a versatile platform for late\u2010stage functionalization relevant to pharmaceuticals, agrochemicals, and materials development.<\/jats:p>","DOI":"10.1002\/anie.7918717","type":"journal-article","created":{"date-parts":[[2026,6,30]],"date-time":"2026-06-30T07:44:40Z","timestamp":1782805480000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Nickel\u2010Catalyzed 1,2\u2010Arylalkenylation of Unactivated Alkenes Enabled by a Native Hydroxy Group"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-9481-2164","authenticated-orcid":false,"given":"Dongping","family":"Wang","sequence":"first","affiliation":[{"name":"Henan Linker Technology Key Laboratory College of Advanced Interdisciplinary Science and Technology Henan University of Technology  Zhengzhou P.R. 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