A systematic investigation of low-lying states of Sc2 using multireference perturbation theory (NEVPT2 and NEVPT3) indicates that the ground state of this system is 5∑u- with r e =2.611 Å, ωe =241.8 cm-1, and De =1.78 eV. This state is closely followed by other low-lying states of Sc2: 3∑u-, 5/Δu, 3Π g, 1Πg, and 1∑u-. Our energy ordering of the 5∑u- and 3 ∑u- states confirms the recent MRCI results of Kalemos [J. Chem. Phys. 132, 024309 (2010)] and is at variance with the earlier diffusion Monte Carlo predictions of Matxain [J. Chem. Phys. 128, 194315 (2008)]. An excellent agreement between the second- and third-order NEVPT results and between the computed and experimental values of ωe (241.8 versus 238.9 cm-1) for the 5∑u- state suggests high accuracy of our predictions.