A straightforward protocol for the synthesis of 11-trifluoromethylated dibenzodiazepines has been developed via TBAC-induced trifluoromethylation/cyclization of o-isocyanodiaryl amines using Togni’s reagent as the trifluoromethyl source. This is the first report on the one-step construction of CF3-containing dibenzodiazepine drug skeletons. Additionally, a series of 11-trifluoromethylated dibenzodiazepines were afforded in moderate to excellent yields under transition-metal-free conditions.