The　selective　hydrogenation　reactions　play　a　key　role　in　industrial　manufacture　of　fine　chemicals,　which　mainly　rely　on　noble　metal　catalysts.　Herein,　a　noble-metal-free　hybrid　photosystem　is　established,　in　which　boron　carbonitride　(BCN)　and　nickel　bis-diphosphine　complex　(NiP)　catalyze　cooperatively　the　semi-hydrogenation　of　alkynes　with　high　efficiency　and　excellent　selectivity　(＞99%)　under　mild　reaction　conditions.　In　the　process,　BCN　catalyst　acts　as　an　“electronic　motor”　and　light　harvester　to　establish　the　electron-　and　hydrogen-atom-delivery-transport　chains　to　molecular　NiP　catalyst,　with　the　ultimate　output　of　reduced　products.　The　work　presents　a　photosystem　that　displays　great　potential　for　further　organic　transformations　with　high　selectivity　via　cooperative　organic　photosynthesis.　©　2022　CCS　Chemistry.　All　rights　reserved.