Scandium-benzene complexes, Sc-(C6H6)1,2 are produced by interactions between the laser-vaporized scandium atoms and benzene vapor in pulsed molecular beams, and identified by photoionization time-of-flight mass spectrometry and photoionization efficiency spectroscopy. The electron-spin multiplicities and geometries of these complexes and their ions are determined by combining pulsed field-ionization zero electron kinetic-energy spectroscopy and density-functional theory calculations. For scandium-monobenzene, a short-range quartet ground state is determined for the neutral complex, and a low-energy triplet state is probed for the ion. For the dibenzene complex, the neutral ground state is a doublet, and two low-energy ion states are singlet and triplet. The quartet and triplet states of scandium-monobenzene and the triplet state of scandium-dibenzene possess sixfold symmetry, whereas the doublet and singlet of the dibenzene complex have twofold symmetry. Moreover, ionization energies and metal-ring stretching wavenumbers are measured for both complexes.