 Binder-free Ni/NiO microwire hybrid network with a nanostructured surface is synthesized by employing a facile and low-cost method, involving one-pot synthesis of Ni microwires, followed by their partial oxidation in air atmosphere. A combination of imaging, diffraction, thermodynamic and electrochemical methods has been applied to reveal the impact of the synthesis conditions on the energy storage performance of the Ni/NiO microwire networks. The thermal conditions for the synthesis have been optimized by means of thermogravimetric (TGA/DSC) analysis, where an appropriate temperature (T = 400 °C) for obtaining a low-defect NiO phase has been determined. The performed electrochemical characterisation of the materials has shown that setting a low temperature for the synthesis enables high reversible capacity and better cycling stability of the binder-free materials. When the Ni/NiO network structures are deposited by a conventional slurry-based technology, involving polymer binder and conductive additive, the high capacity and cycling stability of the anodes are preserved, independent of the temperature conditions of synthesis. Electrochemical impedance spectroscopy is applied to support the interpretation of our results.