The　incorporation　of　alkenylboronates　into　axially　chiral　compounds　increases　their　structural　diversity　and　provides　a　synthetic　handle　for　late-stage　functionalizations.　Despite　advances　made　in　the　synthesis　of　axially　chiral　acyclic　alkenes,　catalytic　enantioselective　synthesis　of　tetrasubstituted　axially　chiral　acyclic　alkenylboronates　still　remains　a　challenge.　Here,　we　report　a　combined　copper-　and　palladium-catalysed　atroposelective　arylboration　of　alkynes,　providing　access　to　tetrasubstituted　axially　chiral　alkenylboronates.　The　process　can　tolerate　a　broad　range　of　functional　groups　and　substrates,　including　unsymmetrical　alkynes,　providing　products　with　excellent　Z-/E-selectivity,　regiocontrol　and　enantiocontrol.　The　synthetic　use　of　the　products　has　been　demonstrated　through　onwards　synthetic　transformations　to　generate　various　new　axially　chiral　olefins　including　axially　chiral　1,3-enynes.　Mechanistic　experiments　reveal　a　potential　combined　copper　and　palladium　catalytic　cycle,　with　the　observed　stereocontrol　originating　from　a　higher-order　active　palladium　catalyst.　A　combined　copper-　and　palladium-catalysed　atropselective　arylboration　of　alkynes　is　reported.　This　method　uses　B2pin2　and　sterically　hindered　aryl　bromides　for　the　stereoselective　and　regioselective　synthesis　of　axially　chiral　tetrasubstituted　alkenylboronates.　Mechanistic　studies　reveal　that　the　stereocontrol　originates　from　a　higher-order　palladium　intermediate.