A series of new N,N'-dialkyl-4,5-dimethylimidazolium cations possessing electron-rich 2-imidazolylidene- or phosphoranylidene-amino substituents has been efficiently synthesized from common precursors, N,N'-dialkyl-4,5-dimethylimidazol-2-ylidenes. The new lipophilic salts obtained have been found to be highly stable towards strong alkali under both biphasic and homogeneous conditions. Their exceptional aqueous base resistance, which has hitherto only been seen with peralkylated polyaminophosphazenium cations, may be attributed to three factors: aromatic stabilization, efficient resonance charge delocalization, and steric protection of the exocyclic nitrogen linkage due to bulky lipophilic N-alkyl substituents.