Lithium metavanadate is monoclinic with a = 10.158(2), b = 8.4175(9), c = 5.8853(9) Å, β = 110.48(2)° and probable space group C2/c. The structure, refined by least-squares to a ωR = 0.033 using 851 reflections, is isotypic with LiAlSi2O6 (spodumene) and LiFeSi2O6. Bands of Li—O edge-shared octahedra run parallel to c and are linked by chains of VO4 tetrahedra which also run parallel to c. The mean Li(1)—O and Li(2)—O distances are significantly different, 2.153(3) and 2.284(3) Å, and are related to the degree of distortion of individual distances from the mean. The V—O distances of 1.821, 1.795, 1.662, and 1.628 Å with a mean value of 1.725 Å are consistent with bond strength sums around the oxygen atoms and empirical bond length – bond strength curves.