Abstract α‐Trifluoromethyl alkenes are versatile CF 3 ‐containing feedstocks. They have been widely used to construct gem ‐difluoroalkene scaffolds through β−F elimination. The application of α−CF 3 alkenes as trifluoromethylating reagents has been less explored. Herein, we report an efficient route for the synthesis of β‐trifluoromethylated ketones from readily accessed α−CF 3 styrenes and aromatic carboxylic acids under photoredox catalysis. The reactions proceed by phosphoranyl radical promoted deoxygenation of aromatic acids, generating acyl radicals for subsequent hydroacylation of α−CF 3 styrenes. The valuable trifluoromethyl‐containing compounds could be produced in good yields under mild conditions.