The deprotonation of HCF3, an industrial waste product, by the super basic phosphazene, {(Et2N)3P = N}3P = NtBu (EtP4), enables the syntheses and characterization of the trifluoromethylchalcogenide salts [EtP4H]+[SeCF3]- and [EtP4H]+[TeCF3]-. These salts were generated through nucleophilic trifluoromethylation of elemental selenium and tellurium. The use of HCF3 as a readily available and cheap CF3 source makes this an efficient and economical approach to trifluoromethylselanide and trifluoromethyltellanide salts. In addition to the structural elucidation of both salts, the reactivity of the selanide salt was explored, whereby the new gallium and indium species, [EtP4H]+[(C2F5)3GaSeCF3]- and [EtP4H]+[(C2F5)3InSeCF3]- were synthesized.