Catalytic　enantioselective　borylation　reactions　of　unsaturated　bonds　as　powerful　tools　for　the　synthesis　of　diverse　chiral　organoboron　compounds　have　gained　much　attention　and　have　wide　applications　in　various　fields.　However,　the　atroposelective　arylboration　reaction　with　carbon-carbon　triple　bonds　of　1,3-enynes　to　obtain　axially　chiral　1,3-dienylboronates　remains　an　elusive　and　significant　challenge.　Hence,　we　develop　a　cooperative　copper-　and　palladium-catalyzed　arylboration　reaction　to　assemble　plentiful　function　enriched　axially　chiral　1,3-dienylboronates　in　a　single　step　from　easily　available　1,3-enynes,　B2pin2,　and　aryl　bromides　with　high　levels　of　chemo-,　regio-,　stereo-,　and　atroposelectivity.　The　mild　reaction　conditions　lead　to　good　functional　group　tolerance,　which　is　proven　by　the　broad　substrate　scope　and　late-stage　functionalizations　of　bioactive　compounds　or　drug　molecules.　Moreover,　the　reaction　can　be　easily　scaled　up,　and　a　series　of　further　transformations　can　be　achieved.　It　is　worth　emphasizing　that　several　olefin　catalysts　and　ligands　with　axial　chirality　can　also　be　synthesized　through　the　corresponding　elaborations　of　such　products,　which　further　explains　the　powerful　transformative　ability　and　application　potential　of　such　axially　chiral　1,3-dienylboronates.　The　mechanism　experiment　and　density　functional　theory　(DFT)　calculations　revealed　the　cooperative　process　of　copper　and　palladium　catalysis,　indicating　that　the　chemoselectivity　and　regioselectivity　of　boration　are　determined　by　the　enyne　insertion　step　on　copper,　and　the　atroposelectivity　is　controlled　by　the　further　reductive　elimination　on　the　palladium　center.　Meanwhile,　the　calculation　also　demonstrated　that　the　distinct　interactions　between　the　P═O　and　C═O　groups　with　the　Pd　or　Bpin　center　in　the　key　transition　state　lead　to　the　formation　of　products　with　varying　configurations　while　employing　identical　configuration　ligands.　©　2024　American　Chemical　Society.