Exohedral cuprofullerenes with 6-, 12-, or 24-nuclearity were obtained by utilizing fluorocarboxylic/dicarboxylic acid under solvothermal conditions. The 24-nuclear molecule presents a C-60@Cu-24 core-shell structure with a rhombicuboctahedron Cu-24 coated on the C-60 core, representing the highest nuclearity in metallofullerene. The resultant complexes show an efficient absorption of visible light as opposed to the pristine C-60. TD-DFT calculations revealed the charge transfer from Cu(I) and O atoms to the fullerene moiety dominates the photophysical process.