According to a first orientating view on the geometrical and electronic structure of the tris(pentafluoroethyl)silanide, this anion appears as aLewisbase. Quantum chemical calculations on perfluoroalkylated silanides show significantly lower HOMO and LUMO energy levels in comparison to their non-fluorinated counterparts, which implies reducedLewisbasicity and increasedLewisacidity of the [Si(C2F5)3]-ion. With these findings and a HOMO LUMO gap of4.80eVsimilar to N-heterocyclic silylenes (NHSi's), perfluoroalkyl silanides are predestinated to exhibitLewisamphoteric character similar to silylenes. Deprotonation of Si(C2F5)3H with sterically demanding phosphazene bases afforded thermally stable phosphazenium salts of the[Si(C2F5)3]-anion, which add to benzaldehyde, benzophenone, CS2and CO2in various manners. This behavior also mirrors the reactivity of silylenes towards ketones as well as heterocumulenes and is rationalized byLewisamphotericity being inherent in these silanides. © 2021 Wiley-VCH GmbH.