The first Cp*Co(III)-catalyzed ortho-C-H perfluoroallylation of aromatic ketones via weakly coordinating ketone-directed C-H activation was developed. This method features good functional group tolerance, high efficiency, and broad substrate scope. A variety of aromatic ketones such as propiophenones, diaryl ketones, and bioactive chalcones were compatible with this catalytic system. Furthermore, mechanistic studies reveal that the C-H activation step may not be involved in the turnover-limiting step.