High-rate and long-cycle life Li-ion batteries constructed with all-manganese-based electrode materials have been successfully realized. The key to the success is the facile green synthesis of the anode: MnO@C core–shell nanowires with internal void spaces and a uniform carbon coating shell. The unique one-dimensional nano-configuration provides reduced solid-state distance for Li-ion/electron transport, enhanced electrical conductivity for charge transfer, and effectively volumetric accommodation for Li-ion insertion/extraction, thus enabling the MnO@C nanostructures to exhibit high-rate Li-ion storage capacity and long cycling stability. When coupled with a nanostructured LiMn2O4 cathode, the all-manganese-based MnO@C∥LiMn2O4 full cell characterizes a high energy density of 397Whkg−1, high rate capability (215Whkg−1 at a power density of 6.2kWkg−1), and an extremely low decay rate of 0.087% per cycle over 1000 cycles. Combining with additional merits of low cost, eco-friendliness, and safe operation, our design will shed light on fabricating high-performance Li-ion batteries from all manganese-based electrode materials.