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.　[Figure　not　available:　see　fulltext.]　©　2023,　The　Author(s),　under　exclusive　licence　to　Springer　Nature　Limited.