Metal-free, metal-like lustrous films may find applications in a variety of fields, and a study of the factors affecting their stability is highly desirable. In particular, chemical events occurring in the coating solutions might affect the supramolecular organization of the films and therefore the metal-like luster. Herein, the chemical events occurring in acetonitrile and nitromethane coating solutions of oligo(3-methoxythiophene) and their effect on the optical properties of the films were investigated by X-ray diffraction, UV-vis absorption, and viscosity measurements. In acetonitrile, the oligomers underwent gradual dedoping with time, but only small changes in viscosity were observed. The solution was applied to a glass plate to yield a dark brown film, which turned into a goldlike lustrous film by rubbing. In nitromethane, the supramolecular structure of the oligomers changed with time from the nonaggregated state to pi-dimers and then to pi-stacks, and the viscosity increased. The properties of the goldlike films prepared from this solution were greatly affected by this chemical event. Remarkably, the pi-dimer solution provided the film with the highest specular reflectance, yellowness, greenness, brightness, and crystallinity.