Gold(I) chloride complexes of arylisocyanides derived from 9‐benzylidene‐9H‐fluorene (Flu), 5‐benzylidene‐1,2,3,4‐tetraphenylcyclopentadiene (TPCp), and 5‐benzylidene‐5H‐dibenzo[a,d]cycloheptene (Dbs) have been prepared. The crystal structures and electronic properties of the three complexes are discussed. UV/Vis data complemented by DFT calculations indicate that the gold(I) centers act as Lewis acids and increase the acceptor strength of the isocyano group. The metal center therefore indirectly affects the optical properties of the π‐conjugated ligands, but is not directly involved in electronic transitions.