Ni-doped MnCO3 microspheres were successfully synthesized via a one-step mixed solvent-thermal method. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N-2 adsorption-desorption measurements. The fabricated Ni-doped MnCO3 microspheres exhibited a higher specific capacity (538 F g(-1) at a current density of 1 A g(-1)) than pure MnCO3 (287 F g(-1)). In addition, 85.8 % of initial capacity was retained after 3000 cycles at a current density of 5 A g(-1), demonstrating a good cycling performance. These results suggested that Ni-doped MnCO3 microspheres material was a promising candidate for high energy storage applications. Hence doping heterogeneous element with good electrical conductivity was an effective approach to improve the electrochemical performance of the electrode materials.