Single-phase LiVO3 with a monoclinic structure (S.G. C2/c) was prepared by mechanochemically assisted solid state synthesis using V2O5 and Li2CO3 as raw materials. The reagent mixtures, activated by means of a high-energy planetary mill AGO-2, were annealed at 350, 450 and 550 degrees C in air. Thus-prepared LiVO3 samples were characterized by XRD using the Rietveld refinement, SEM, TEM, HRTEM, FTIR, Raman spectroscopy, Li-6 and V-51 MAS NMR spectroscopy, XPS, galvanostatic cycling, and GITT. The average particle size increases from similar to 100 nm for LiVO3-350 degrees C to some micrometers for LiVO3-550 degrees C along with the degree of crystallinity. XRD, FTIR, Li-6 and V-51 MAS NMR reveal the largest degree of structural distortion for the LiVO3-350 degrees C sample. Ex situ XRD confirms a biphasic mechanism of the initial lithium intercalation in LiVO3 and a single-phase mechanism for a fully lithiated Li2VO3. The rock salt type structure of Li2VO3 (S.G. Fd-3m) keeps unchanged during the following cycling; a lattice parameter a increases upon delithiation from 8.22 angstrom to 8.29 angstrom(2.5%). According to XPS, lithiation of LiVO3 is accompanied by V5+/V4+ redox couple. The nanosized LiVO3-350 degrees C sample exhibits the largest initial discharge capacity (317 mA h g(-1)), however followed by a progressive decay due to the presence of structural distortion. On the contrary, LiVO3-450 degrees C sample is characterized by better capacity retention and high-rate performance. The average value of Li-ion diffusion coefficient determined from the GITT measurements is the 10(-12) cm(2) s(-1); it does not noticeably change vs. Li content. (C) 2015 Elsevier Ltd. All rights reserved.