α‐Trifluoromethyl alkenes are versatile CF3‐containing feedstocks. They have been widely used to construct gem‐difluoroalkene scaffolds via β‐F elimination. The application of α‐CF3 alkenes as trifluoromethylating reagents has been less explored. In this paper, we report an efficient route for the synthesis of β‐trifluoromethylated ketones from easily‐accessed α‐CF3 styrenes and aromatic carboxylic acids under photoredox catalysis. The reactions proceed through phosphoranyl radical‐promoted deoxygenation of aromatic acids, generating acyl radicals for subsequent hydroacylation of α‐CF3 styrenes. The valuable trifluoromethyl‐containing compounds could be produced in good yields under mild conditions.