A novel composite of layered lithium-rich oxide, Li-Rich@Li3PO4, coated with Li3PO4 is synthesized through polydopamine template method. Physical characterizations reveal that Li-Rich@Li3PO4 is composed of nanoparticles of 100–200 nm that are coated with a uniform Li3PO4 layer of about 5 nm in thickness. Galvanostatic charge/discharge tests demonstrate enhanced cycling stability and largely increased rate capability of the material after Li3PO4 coating.