A Ni-catalyzed reductive dicarbofunctionalization of α-CF3 styrenes with benzyl bromides has been accomplished. This transformation obviates the commonly facile β-F elimination effectively and enables the creation of CF3-substituted all-carbon quaternary centers of pharmaceutical interests. Preliminary mechanistic studies suggest a pathway consisting of benzyl radical addition and subsequent nickel-mediated benzylation of the resulting α-CF3-embedded tertiary C radical.