N-Fluoroquinuclidinium fluoride, prepared in high yield by treatment of a cold, dilute solution of quinuclidine in trichlorofluoromethane with fluorine at low pressure in a specially designed, virtually all glass vacuum system, acts as a site-selective electrophilic fluorinating agent towards carbanionic substrates [PhCNa(CO2Et)2→ PhCF(CO2Et)2; Me2CLiNO2→ Me2CFNO2; RMgX → RF (R = Ph, X = Br; R = c-C6H11, X = Cl); [graphic omitted]H2→ [graphic omitted]HF; PhSiCl3/F–(in situ)→ PhF].