Chiral　five-membered　cyclic　tertiary　alcohols　are　important　structural　motifs　in　functional　materials,　pharmaceuticals,　and　bioactive　molecules.　Hence,　developing　efficient　methodologies　for　synthesizing　compounds　featuring　these　privileged　scaffolds　represents　a　crucial　pursuit　within　synthetic　chemistry.　Herein,　we　present　a　regio-　and　enantioselective　Ni-catalyzed　strategy　for　the　reductive　[3 + 2]　annulation　of　β-bromoenones　with　alkynes,　providing　convenient　access　to　chiral　five-membered　cyclic　tertiary　alcohols　with　high　levels　of　regio-,　and　enantioselectivity　via　axial　chirality　transfer　to　central　chirality.　The　utilization　of　an　environmentally　sustainable　bis(pinacolato)diboron　(B2pin2)　is　crucial　for　the　success　of　this　asymmetric　reductive　cyclization　reaction.　Simultaneously,　the　mild　reaction　environment　greatly　enhances　functional　group　compatibility.　This　has　been　demonstrated　by　the　broad　substrate　scope,　late-stage　functionalizations　of　bioactive　compounds　or　drug　molecules,　and　subsequent　transformations.　Amongst,　it　is　worth　emphasizing　that　these　functionally　enriched　chiral　five-membered　cyclic　tertiary　alcohols　can　efficiently　participate　in　Diels–Alder　reactions　to　synthesize　enantioenriched　polycyclic　and　heterocyclic　molecules,　thereby　further　validating　the　significance　of　introducing　a　cyclopentadiene　skeleton.　The　preliminary　mechanistic　studies　revealed　the　mode　of　action　of　B2pin2　in　mononuclear　Ni-catalyzed　asymmetric　reductive　[3 + 2]　annulation　reactions　and　density　functional　theory　(DFT)　calculations　clarified　the　origin　of　the　experimentally　observed　regio-　and　enantioselectivity.　©　2025　Wiley-VCH　GmbH.