The trifluoromethanide anion is the postulated key intermediate in nucleophilic trifluoromethylation reactions. However, for more than six decades, the trifluoromethanide anion was widely believed to exist only as a short‐lived transient species in the condensed phase. It has now been prepared in bulk for the first time in THF solution. The trifluoromethanide anion with the [K(18‐crown‐6)]+ cation was unequivocally characterized by low‐temperature 19F and 13C NMR spectroscopy. Its intermediacy in nucleophilic trifluoromethylation reactions was directly evident by its reaction chemistry with various electrophilic substrates. Variable‐temperature NMR spectroscopy, along with quantum mechanical calculations, support the persistence of the trifluoromethanide anion.