Lithium metavanadate (LiVO₃) single crystals have been studied by Raman spectroscopy under high pressure up to 200 kbar. Three phase transitions were observed and they are believed to be a series of transitions involving the breaking up of the infinite VO₄^- chains into VO₃^- ions of average symmetry C_{3 nu}. On decompression, the LiVO₃ transforms into an amorphous phase instead of reverting to the ambient crystalline phase, similarly to what has been observed for alpha -NaVO₃. The difference in the behaviours between LiVO₃ and alpha -NaVO₃ on compression has been explained by the different sizes of the Li⁺ and Na⁺ ions. The restoration of the virgin crystalline phase and the relinking of the VO₄^- chains were observed after heating the reclaimed samples.