Cobalt-catalyzed enantioconvergent cross-coupling of α-bromoketones with aryl zinc reagents is achieved to access chiral ketones bearing α-tertiary stereogenic centers with high enantioselectivities. The more challenging and sterically hindered α-bromoketones bearing a 2-fluorophenyl group or β-secondary and tertiary alkyl chains could also be well-tolerated. Adjusting the electronic effect of chiral unsymmetric N,N,N-tridentate ligands is critical for improving the reactivity and selectivity of this transformation, which is beneficial for further studies of asymmetric 3d metal catalysis via ligand modification. The control experiments and kinetic studies illustrated that the reaction involved radical intermediates and the reductive elimination was a rate-determining step.