AbstractThe first coordination‐saturated buckyball with a C₆₀ molecule totally encased in an icosidodecahedral Cu₃₀ in a (μ₃₀‐(η²)₃₀)‐fashion, namely C₆₀@Cu₃₀@Cl₃₆N₁₂, has been successfully realized by a C₆₀‐templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (Cu^I, Cl) to C₆₀ explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry.