We studied lithium azide (LiN(3)) by x-ray diffraction and Raman spectroscopy at hydrostatic compression up to pressures above 60 GPa at room temperature. The results of x-ray diffraction analyses reveal the stability of the ambient-pressure C 2/m crystal structure up to the highest pressure. The pressure dependence of librational modes provides evidence for an order-disorder transition at low pressures (below 3 GPa), similar to the transition observed previously at low temperatures. The observed structure stability indicates that this transition is not associated with structural changes. The phase stability of LiN(3) is in contrast to that of sodium azide (which is isostructural at ambient pressure), for which a set of phase transitions has been reported at pressures below 50 GPa.