The presented flow strategy enables the generation of reactive NCF3(PG), SCF3, and OCF3 anions from bench stable organic precursors using cesium fluoride as the sole fluorine source. These nucleophilic species are generated on-demand and subsequently reacted with a wide variety of electrophiles under different substitution pathways, including natural-derived products and advanced API intermediates. In the case of the NCF3 fragment, we disclose a new disconnection for the incorporation of this motif into Csp 3 electrophiles. Based on our findings, we anticipate that this system will be useful for the divergent preparation of heteroatom trifluoromethyl molecules in both academic and industry contexts. Importantly, our strategy avoids the use of environmentally threatening perfluoroalkyl materials, thereby opening the door to a more sustainable synthesis of fluorochemicals.