Highly linear selective, imine-directed hydroarylation of styrene has been achieved with cobalt-based catalytic systems featuring bis(2,4-dimethoxyphenyl)(phenyl)phosphine and either 2-methoxypyridine or DBU as a ligand and a Lewis base additive, respectively, thus affording a variety of 1,2-diarylethanes (bibenzyls) in good yields under mild reaction conditions. The triarylphosphine controls the regiose- lectivity, while the Lewis base significantly accelerates the reaction. Ligand screening and deuterium-labeling studies provide implications about the roles of the ligand and the Lewis base in the crucial C-C reductive elimination step.