Synthesis of CF3-containing compounds is of great interest because of their broad use in the pharmaceutical and agrochemical industries. Herein, selective 2,2,2-trifluoroethylation of styrenes was catalyzed by Zr(IV)-based MOFs bearing visible-light photocatalysts in the form of Ir(III) polypyridyl complexes. When compared to the homogeneous Ir(III) catalyst, the MOF-based catalyst suppressed the dimerization of benzyl radicals, thus enhancing the selectivity of the desired hydroxytrifluoroethyl compounds.