An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified.This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as “Volleyballene”.Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure.A relatively large HOMO–LUMO gap(~1.4 eV)was found.The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.