The direct upgrading reaction of simple and readily available achiral alcohols via C-H functionalization is an ideal strategy to prepare value-added chiral higher alcohols. Herein, we disclose the first enantioconvergent upgrading reaction of simple racemic secondary alcohols to enantioenriched tertiary alcohols. An N-heterocyclic carbene (NHC)-nickel catalyst was leveraged to enable this highly efficient formal asymmetric alcohol α-C-H arylation via a dehydrogenation using phenyl triflate as a mild oxidant followed by asymmetric addition of arylboronic esters to the transient ketones. Mechanistic studies and control experiments were conducted to reveal the possible reasons for the exceptional control over chemo- and enantioselectivity.