The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer LSi:2 (1; L=PhC(NtBu)2) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate 4‐NMe2C5H4NSiMe3OTf and two equivalents of DMAP in THF afforded LSi(DMAP)OTf (2). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate L′2(L)SiOTf (3; L′=LSi:) with the displacement of DMAP. The reaction of 2 with K{HB(iBu)3} and elemental sulfur in THF afforded the silylsilylene LSiSi(H){(NtBu)2C(H)Ph} (4) and the base‐stabilized silanethionium triflate LSi(S)DMAPOTf (5), respectively. Compounds 2, 3, and 5 have been characterized by X‐ray crystallography. 1 becomes 2: The singlet silyliumylidene cation 2, which is stabilized by both an amidinate ligand and 4‐dimethylaminopyridine (DMAP), can be synthesized by the reaction of the amidinate SiI dimer 1 with N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate and DMAP (see scheme). The ambiphilic character of 2 can be demonstrated by its reactivity.