This review provides a recent overview of the different synthetic routes of the N‐CF3 group. This scaffold can be prepared from the desulfurization of thiocabamoyl fluorides or isothiocyanates with fluoride ions. Electrophilic and radical trifluoromethylations are also a great way to generate this motif. This report also focuses on the valorization of some N‐CF3 compounds, which leads to new unknown N‐trifluoromethyl derivatives. Finally, the first metabolic stability studies will be given for certain structures.