We report on rational design and synthesis of mesoporous three-dimensional (3D) hierarchical Cu-doped NiO architectures with adjustable chemical component, surface area, and hierarchically porous structure.The effect of Mn doping and calcining temperature on the microstructure, surface area, porous structure of the 3D mesoporous Cu-doped NiO nano-architectures is investigated using SEM, TEM, XPS, XRD, nitrogen adsorption-desorption isotherm techniques. The electrochemical performance of the Cu-doped NiO architectures is studied via cyclic voltammetry (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) techniques. The 3D mesoporous Cu-doped NiO hierarchical architectures display greatly enhanced electrochemical performance of high reversible capacity, high-rate capability, and excellent cycling performance as LIBs anode materials. The improved performance of 3D mesoporous Cu x NiO anodes can be attributed to the synergetic effects of an optimal level of Cu doping and hierarchically porous feature. The doping of Cu greatly improves charge transport kinetics at the interface between the electrode and electrolyte, and hierarchically porous structure provides larger surface area and allows for effective electrolyte penetration, alleviates the strain induced by volume excursion in cycle processes. 12 attributed to electrolyte decomposition and the formation of a SEI layer. At the 5 th cycle, it is shown that the Cu 3% NiO electrode shows the best electrochemical performance, displaying the reversible charge capacity of 781, 950, 984 and 826 mA h g -1 (for 0, 1, 3, 5% Cu content), corresponding to coulombic efficiency of 96.9, 97.1, 98.5, 98.1%, respectively. With the increase of Cu doping content, the reversible capacity of the Cu x NiO samples first rapidly increases and then decreases as Cu doping molar percentage is up to 3%. Moreover, the two distinct voltage plateau can be observed clearly at around 0.5 V and 2.2 V corresponding to the initial cathodic and anodic peaks during the CV process described in Fig. 8.The chemical composition component and the microstructures such as grain size, crystallinity, porous structure, surface area and pore volume should impose key effects on the electrochemical performance of the mesoporous 3D hierarchical Cu x NiO architectures. For the effect of Cu incorporation content on the cycling performance and stability, at a galvanostatic charge/discharge current of 100 mA g -1 between 0.01 and 3.0 V, it can be comparatively illustrated in Fig. 10a. Among the Cu x NiO samples with different Cu incorporated contents, the Cu 3% NiO sample delivers the highest specific capacity of 550 mA h g -1 after 100 cycles with a coulombic efficiency of 97.1%. By a comparison, the pure NiO and the Cu 1% NiO, Cu 5% NiO electrode could only display reversible charge capacity of 184 and 376, 272 mA h g -1 after 100 cycles, respectively. It is clearly shown that the reversible capacity of Cu 3% NiO after 100 cycles at a current density of 100 mA h g -1 is 2.98 and 2.0 ti...