Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost‐effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo‐ and organometal‐catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles. A myriad of biologically and pharmaceutically active molecules featuring a heterocyclic segment with a CCF3 stereogenic center are springing up, and some of them have been employed at the clinic stage. This review article describes recent progress on the manufacture of heterocycles possessing a CF3 group at the stereogenic carbon center, prepared from catalytic asymmetric reactions.