Recently the (2)A' ground state has been reported for Ga2P and Ga2As [7], however, there is no previous work on the C-s structure state of Al2As. This Letter reports the geometry optimisations and vibrational frequency calculations performed, using various approaches. In this study, the global minimum belongs to the (2)A' state, correlating with the B-2(2) state. The (2)A(1) state is also reported for the first time. Difficulties in treating the B-2(2) state are discussed in terms of the Hartree-Fock instability. Based on our calculations, we discuss the Al2As photoelectron spectrum. (C) 2011 Elsevier B.V. All rights reserved.