A highly general and selective Co-catalyzed biaryl coupling through C–F cleavage under phosphine or NHC-free conditions was described. A broad range of aryl fluorides including unactivated fluorides as well as those with sensitive functionalities could couple with various Ti(OEt)4-mediated aryl Grignard reagents with high selectivity under the catalysis of CoCl2/DMPU. Importantly, selective C–F bond activation couplings between two types of fluorines (difluorinated aromatics and on two different coupling partners) and in the presence of C–Cl or C–Br bonds could also be achieved.