Superatomic molecular orbitals (SAMOs) have symmetries (angular quantum numbers) similar to those of atoms, and thus, it is possible to realize Rydberg state excitations (RSEs) in superatomic molecules. In this Letter, the feasibility of superatomic Rydberg state excitation (SRSE) is explored using gold superatoms based on first-principles calculations. The results show that the SRSE exists in the high and low excited states of the gold superatoms and their SAMOs make a major contribution to electronic transitions. The radial distribution function of electronic density shows that the main distribution of electrons in the lowest unoccupied molecular orbitals and other unoccupied superatomic molecular orbitals is extremely far from the geometric center, and thus, they can be unambiguously identified as Rydberg orbitals. We found that due to the two-dimensional ductility of the planar SAMOs, superatoms are superior in the RSE regulation. Our findings may provide a new source of superatom-based RSE and will contribute to the regulation and efficient preparation of Rydberg states.