The structure of the lithium metavanadate LiVO 3 has been refined at room temperature from high-resolution neutron powder diffraction data. The unit cell dimensions are a=10.1597 (4) , b=8.4155 (3) , c=5.8843 (2) Å, β=110.505° (2) , and V=471.23 (1) Å 3 in the monoclinic space group C2/c with Z=8. Conventional R p and R wp reliability factors are respectively equal to 0.030 and 0.036. The structure consists of an alternating, along the b-axis, of bands of distorted LiO 6 octahedra running parallel to the c-axis which are linked by chains of VO 4 tetrahedra which are also parallel to the c-axis. The structural behavior of the ionic conductor LiVO 3 has been studied from neutron powder thermodiffractometry in the temperature range 340–890 K in order (i) to confirm the nature of the mobile species, (ii) to characterize the diffusion mechanisms, and (iii) to link the structural disorder existing in LiVO 3 to the high observed ionic conductivity.