A large set of electronic states of scandium dimer has been calculated using high-level theoretical methods such as quantum diffusion Monte Carlo (DMC), complete active space perturbation theory as implemented in GAMESS-US, coupled-cluster singles, doubles, and triples, and density functional theory (DFT). The 3Sigmau and 5Sigmau states are calculated to be close in energy in all cases, but whereas DFT predicts the 5Sigmau state to be the ground state by 0.08 eV, DMC and CASPT2 calculations predict the 3Sigmau to be more stable by 0.17 and 0.16 eV, respectively. The experimental data available are in agreement with the calculated frequencies and dissociation energies of both states, and therefore we conclude that the correct ground state of scandium dimer is the 3Sigmau state, which breaks with the assumption of a 5Sigmau ground state for scandium dimer, believed throughout the past decades.