We report on uniform Li₃V₂(PO₄)₃ microspheres with a size distribution of 1–3 μm assembled with nanoparticles embedded in a carbon matrix. LVP particles have a size of about 50–100 nm and carbon accounts for about 6% in total mass for the one with the best electrochemical performance. An initial capacity of 121 mA h g⁻¹ or 101 mA h g⁻¹ was achieved when cycled at 1 C or 10 C at room temperature with an admissible capacity fading of 8% after 100 cycles. The high rate capability and cycling stability may attribute to the unique microsize, electron conductive continuous carbon matrix and stable 3D skeleton of Li₃V₂(PO₄)₃.