UiO-66(Zr),　a　UV-responsive　Zr-based　metal-organic　framework　(MOF)　material,　is　found　to　be　highly　active　and　chemoselective　for　the　visible-light-initiated　acceptor-less　dehydrogenation　of　alcohols　to　coproduce　vicinal　diols　and　H2.　The　formation　of　a　colored　surface　alkoxide　complex　between　alcohols　and　UiO-66(Zr)　enables　the　UV-responsive　UiO-66(Zr)　to　be　active　under　visible　light,　while　the　formation　of　a　hydrogen　bond　between　alcohols　and　μ3-OH　in　UiO-66(Zr)　is　responsible　for　its　high　selectivity　to　vicinal　diols.　The　elucidation　of　the　involved　mechanism　will　provide　some　guidance　for　the　controllable　syntheses　of　vicinal　diols　and　aldehydes,　a　very　important　reaction　in　the　chemical　industry,　via　the　visible-light-initiated　acceptor-less　dehydrogenation　of　alcohols.　©　2022　American　Chemical　Society.　All　rights　reserved.