Chiral　sulfinamides　find　broad　applications　in　bioactive　compounds,　chiral　auxiliaries,　chiral　ligands,　and　organocatalysts.　However,　biocatalytic　approaches　for　their　enantioselective　synthesis　have　rarely　been　explored.　Herein,　an　efficient　biocatalytic　strategy　for　the　synthesis　of　chiral　sulfinamides　via　polycyclic　ketone　monooxygenase　(PockeMO)　catalyzed　asymmetric　oxidation　of　sulfenamides　was　reported.　A　diverse　array　of　chiral　sulfinamides　can　be　readily　accessed　with　high　yields　(up　to　＞99%)　and　enantioselectivities　(＞99:1　er).　Additionally,　this　biocatalytic　platform　was　scalable,　and　the　resulting　synthetic　chiral　sulfinamides　could　be　easily　derivatized　to　various　chiral　S-stereogenic　compounds.　Molecular　dynamics　simulation　studies　revealed　that　hydrogen　bonding　interactions　between　the　sulfenamides　and　key　residues　were　essential　for　enantioselectivity　control.　This　work　unlocks　a　biocatalytic　avenue　to　access　chiral　sulfinamides　for　synthetic　chemistry　and　drug　discovery.　©　2025　American　Chemical　Society