Fullerenes, with well-defined molecular structures and high scalability, hold promise as fundamental building blocks for creating novel carbon materials.1–3 The fabrication and transfer of large-area films with precisely controlled thicknesses and morphologies on desired surfaces are crucial for designing and developing new fullerene-based materials and devices.4,5 Here we demonstrate the preparation of centimetre-wide graphene/C60/graphene heterostructures through layer-by-layer stacking of C60 and CVD-grown graphene films. We have successfully performed the complete transfer of chemically modified C60 films, including oxygenated C60 films and C60Pdn organometallic polymer films, allowing their electrocatalytic performance to be probed directly. Furthermore, we have achieved freestanding C60 films with thicknesses as low as 20 nm. This versatile transfer strategy6 facilitates the facile preparation and transfer of large-area C60 films, offering a distinct platform for fullerene chemistry and experimental synthesis of novel carbon structures.