We provide evidence that a heteroleptic double-decker complex of Ce with phthalocyanine and porphyrin ligands undergoes rotational libration in solution for the first time on the basis of variable-temperature H-1 NMR. On the other hand, the Zr complex with the same set of ligands undergoes no rotational motion. These molecules deposited on graphite surfaces exhibited different shapes in STM images, revealing difference in the rotational motion at the molecular level.