Building upon the success of the flow system for the NCF3(PG) anion generation, we proceeded to investigate the incorporation of chalcogen-based trifluoromethyl fragments following our overarching on-demand generator strategy. The trifluoromethylthio (SCF3) and trifluoromethoxy (OCF3) groups are both of significant interest due to their potential as lipophilic modulators for the fine-tuning of active pharmaceutical ingredients. For the on-demand flow generation of trifluoromethylthiolate anions ([SCF3] -), thiophosgene 41 was selected as the precursor owing to its commercial availability, cost-effectiveness, and extensive industrial application on the ton-scale. In the case of the trifluoromethoxy anions ([OCF3] -) we opted for diphosgene 42 as the precursor, as it is widely used as a more convenient alternative to toxic and gaseous phosgene in various carbonylation reactions. Analogous to the process with protected imidoyl dichlorides, the reaction with cesium fluoride and our selected precursors would initially produce gaseous thiocarbonyl or carbonyl fluoride intermediate, respectively. However, the enclosed flow system ensures that these intermediates rapidly undergo further reaction with another fluoride ion, leading to the rapid and complete formation of the desired trifluoromethyl-chalcogen anions, thus mitigating any potential safety risks. After a brief optimization (see the Supplementary Information), we successfully generated both chalcogen-trifluoromethyl nucleophiles in our system with a residence time as short as 5 minutes for the trifluoromethylthiolate anion, and 7 minutes for the trifluoromethoxy one. With these results in hand, we proceeded to evaluate a diverse scope of electrophilic partners.