Chiral　phosphorus-containing　compounds　find　applications　across　various　fields,　including　asymmetric　catalysis,　medicinal　chemistry,　and　materials　science.　Despite　the　abundance　of　reported　highly　enantioselective　methods　for　synthesizing　various　chiral　phosphorus　compounds,　the　enantioselective　synthesis　of　α-boryl　phosphorus　compounds　still　remains　an　unknown　territory.　Here,　we　report　a　method　for　the　construction　of　chiral　α-boryl　phosphates　by　asymmetric　B-H　insertion　reaction　using　α-diazo　phosphates　as　carbene　precursors,　cheap　and　readily　available　copper　salt　as　the　catalyst　and　chiral　oxazoline　as　the　ligand.　This　method　can　directly　afford　a　series　of　stable　α-boryl　phosphates　with　a　yield　up　to　97%　and　an　enantioselectivity　up　to　98%　ee.　The　operating　procedure　of　this　method　is　straightforward,　offering　a　broad　substrate　applicability,　remarkable　tolerance　towards　various　functional　groups,　and　gentle　reaction　conditions.　©　2024　The　Royal　Society　of　Chemistry.