Recent advances in the synthesis of trifluoromethyl or trifluoroacetyl substituted heterocyclic compounds by use of trifluoromethyl‐α,β‐ynones are summarized. Seven approaches will be reviewed and divided into (a) synthesis of trifluoromethyl‐pyridines, trifluoromethyl‐quinolines, and trifluoroacetyl‐quinolines; (b) synthesis of trifluoromethyl‐oxazinopyridines and trifluoromethyl‐oxazinoquinolines; (c) synthesis of trifluoromethyl‐pyrazoles, trifluoromethyl‐isoxazoles, and trifluoromethyl‐pyrazolo[1,5‐a]pyridines; (d) synthesis of trifluoromethyl‐pyrroles, trifluoromethyl‐thiophenes, trifluoromethyl‐dihydrofurans, and trifluoromethyl‐isochromanone; (e) synthesis of trifluoromethyl‐pyrimidines, (f) synthesis of trifluoroacetyl‐1,2,3‐triazoles; (g) synthesis of trifluoromethyl‐aziridines and trifluoromethyl‐[1,4]diazepines.