Abstract The incorporation of the trifluoromethylselenyl (CF 3 Se) group has become a prominent area of research in recent years because of its high electron‐withdrawing capacity, excellent lipophilicity, good stability, and favorable bioavailability. These properties make CF 3 Se a promising structural motif for drug design and development. Among the various methods for synthesizing CF 3 Se‐containing compounds, trifluoromethylselenofunctionalization of unsaturated C─C bonds has emerged as a powerful strategy for the preparation of these compounds because this process facilitates the introduction of the CF 3 Se motif as well as other functional groups into unsaturated C─C bonds. In this review, we summarize recent advancements and achievements in the trifluoromethylselenofunctionalization of multiple C─C bonds. For clarity, the reactions were classified according to the type of functional groups introduced. Additionally, this review highlights the mechanistic aspects of these reactions, which may inspire further work in this appealing research field.