A quantum chemical investigation of the clusters Li5B, Li6B+, Li6B and Li7B was performed using the DFT, MP2 and CCSD(T) methods. The high symmetry structures (C-4v, (1)A(1)), (Oh, (1)A(1g)) and (D-5h, (1)A'(1)) turnout to be the global minima for Li5B, Li6B+ and Li7B, respectively. These clusters are predicted to be highly stable species with large vertical ionization energies, and large HOMO-LUMO gaps. Chemical bonding of clusters was probed using an electron localizability indicator (ELI) which indicates a large aromatic character. The high stability of these clusters can be accounted for by the phenomenological shell model. (C) 2010 Elsevier B.V. All rights reserved.