Abstract. Attempted syntheses of AgR f ·DMAP were performed using the established route starting from AgF and Me 3 SiR f (R f = CF 3 , C 2 F 5 , C 6 F 5 ) followed by the addition of DMAP. Unexpectedly, reactions with perfluoroalkylsilver(I) derivatives yielded products, which underwent known equilibria, while exclusively the pentafluorophenyl derivative exhibits its zwitterionic nature in solution and in the solid state. Moreover, both perfluoroalkyl derivatives investigated decomposed slowly