Results of computational investigations of the structural and electronic properties of the ground states of binary compounds LiB x with 0.67 ≤x≤1.00 under pressure are reported. Structure predictions based on evolutionary algorithms and particle swarm optimization reveal that with increasing pressure, stoichiometric 1:1-LiB undergoes a variety of phase transitions, is significantly stabilized with respect to the elements and takes up a diamondoid boron network at high pressures. The Zintl picture is very useful in understanding the evolution of structures with pressure. The experimentally seen finite range of stability for LiB x phases with 0.8≤x≤1.00 is modeled both by boron-deficient variants of the 1:1-LiB structure and lithium-enriched intercalation structures. We find that the finite stability range vanishes at pressures P≥40GPa, where stoichiometric compounds then become more stable. A metal-to-insulator transition for LiB is predicted at P = 70 GPa. © 2012 American Physical Society.