Improving the charge capacity, electrochemical reversibility and stability of anode materials are main challenges for the development of Ni-based rechargeable batteries and devices. The combination of cobalt, as additive, and electrode material nanostructuration revealed a very promising approach for this purpose. The new α-NiCo mixed hydroxide based electrodes exhibited high specific charge/discharge capacity (355–714 C g−1) and outstanding structural stability, withstanding up to 700 redox cycles without any significant phase transformation, as confirmed by cyclic voltammetry, electrochemical quartz crystal microbalance and X-ray diffractometry. In short, the nanostructured α-NiCo mixed hydroxide materials possess superior electrochemical properties and stability, being strong candidates for application in high performance batteries and devices.