In organometallic chemistry, fulvalene is emerging as a promising ligand, despite its inherent instability as a nonaromatic compound composed of both aromatic and antiaromatic rings, which complicates its handling and stability. Although research has been conducted on substituted fulvalenes, significant improvements in their stability remain elusive, particularly with no existing fulvalene structures substituted with N-heterocycles. To address this challenge, we synthesized new fulvalene molecules substituted with imidazolium and pyrrolinium, successfully isolating an imidazolium-substituted zwitterionic fulvalene (IZFv).1,2 These compounds were characterized using NMR, HRMS, X-ray crystallography, and DFT calculations. Notably, IZFv exhibits a planar structure with an extended conjugated system and demonstrates stability under ambient inert conditions, with enhanced aromaticity confirmed by NICS calculations. Furthermore, metalation reactions with IZFv and various transition metals yielded corresponding metalated compounds. These results indicate that IZFv, as a ligand, facilitates the synthesis of both monoatomic and diatomic homonuclear metal complexes, as verified by NMR, HRMS, and X-ray crystallography.