We utilized the phase transformation of C60 molecules to develop a new approach for the preparation of transparent electroconductive films on glass substrates. In this study, the effect on film formation of ultraviolet (UV) irradiation in different atmospheres and in the presence of different metal catalysts was investigated. UV irradiation of the C60 films caused phase transformation by either polymerization or decomposition of C60 molecules depending upon the atmosphere. In the presence of a Ni catalyst, an optically transparent film with graphitic structure was formed. The electrical resistivity of the film was on the order of 10−4 Ω cm. The polymers of C60 molecules by UV irradiation in vacuum played a role as a solid carbon source and as a reductant, and the optically transparent graphitic film was formed by the surface reaction with C60 and the Ni catalyst on the glass substrate. In contrast, in the case of a Cu catalyst, although a film with a resistivity on the order of 10−6 Ω cm was formed, it was almost opaque and showed an undeveloped graphitic structure. A transparent film with a rough surface structure was obtained when UV irradiation was carried out at 500 W for 24 h in ambient atmosphere. In this case, interestingly, Raman spectrum mapping revealed that the region with graphitic structure was separated from the area of the Cu catalyst. It is believed that once the graphitic structure was formed on the Cu catalyst, the catalyst migrated.