Abstract: The Barbier reaction is a reductive-type addition of an aldehyde or ketone with an organic electrophile in thepresence of a terminal metal reductant, providing a straightforward and efficient method for carbon−carbon bond formation. Thisreaction possesses the advantage of circumventing the preparation of moisture- and air-sensitive organometallic reagents. However,the catalytic Barbier reaction of ketones to construct tetrasubstituted stereogenic centers is largely underdeveloped, despite its greatpotential for accessing synthetically challenging chiral tertiary alcohol. Particularly, the leveraging of unactivated alkyl electrophiles ascoupling components is still rarely exploited. Herein, we disclose a photoredox-assisted cobalt-catalyzed asymmetric alkylativeBarbier-type addition reaction of ketones to address the aforementioned challenges, thereby allowing for the construction of highlycongested tetrasubstituted carbon centers. The alkyl addition fragments could be either readily accessible unactivated alkyl halides orredox-active esters generated through a decarboxylative pathway. Both types of alkyl electrophiles include primary, secondary, andtertiary ones, thus affording diverse enantioenriched tertiary alcohols with a broad substrate scope. This enantioselective protocol isapplied for the expedient synthesis of core structure of Sofdra, a very recent FDA-approved drug in 2024. The newly developedbisoxazolinephosphine (NPN) ligand enables high enantioselectivity in this asymmetric reductive addition process.