Asymmetric Ni-catalyzed cross-coupling reactions have become a very attractive tool for the stereoselective construction of valuable organic chiral materials. While various nucleophiles are used in such transformation, organotitanium(IV) has not been used before. Herein we demonstrate, for the first time, that organotitanium species can serve as efficient coupling partners in asymmetric cross-couplings, which have proven to be beneficial, compared to the commonly used organomagnesium and organozinc counterparts. This principle is exemplified by the first asymmetric catalytic synthesis of CF3-substituted thioethers via a Ni-catalyzed stereoconvergent cross-coupling reaction. Thioether moieties and their derivatives are common motifs in many biologically active compounds, and their enantioenriched fluorinated analogs should be of great interest in the search for novel drugs and agrichemicals.