The potential energy surface of the reaction Li(S-2/(2)p) + BO(X(2)Sigma (+)) was investigated theoretically using multireference variational methods in conjunction with flexible correlation consistent basis sets. On the groundstate singlet surface ((X) over tilde (1)A'), three practically degenerate minima were detected, two linear Li-BO and Li-OB (XIII) and one bent Li-OB ((X) over tilde (1)A'), the latter formally being the global one. An energy barrier of about 10 kcal/mol was found to separate the two linear configurations. Potential energy curves of excited singlet and triplet linear states were also examined. The involvement of the ionic interacting fragments Li+(S-1) + BO-(X(1)Sigma (+)) seems to affect all states via avoided crossings, giving rise to highly ionic equilibrium states, particularly in the Li-OB isomer. As a result, the Li atom rotates freely around the O-site of BO moiety within a LiOB angle from 100 degrees to 180 degrees.