The brannerite-type vanadate LiMoVO₆ was prepared by different synthetic methods including the solid-state reaction of oxides and wet chemistry techniques in aqueous solution. The physicochemical and electrochemical properties of the LiMoVO₆ products were extensively investigated. Thermal (TG-DTA) analyses and XRD data showed that powders with a quasi-layered structure (C2/m space group) were obtained at temperatures below 400 °C by the acidification reaction of aqueous solutions. The local structure was characterized by Raman scattering, FTIR and ⁷Li solid state MAS NMR. The discharge–charge profiles were evaluated in rechargeable Li/LiClO₄ + PC/LiMoVO₆ cells and chemical diffusion coefficients of Li⁺ ions were estimated. Lithium insertion in Li_1 + xMoVO₆ positive electrodes fired at 550 °C exhibited an initial capacity retention of ≈200 mA h g⁻¹ which declines rapidly upon charge–discharge cycling. Upon cycling, incremental capacity and Raman features show the instability of the brannerite lattice with the appearance of the Li₂MoO₄ product.