In this study,coral-like yolk-shell-structured NiO/C composite microspheres (denoted as CYS-NiO/C) were prepared using spray pyrolysis.The unique yolk-shell structure was characterized,and the formation mechanism of the structure was proposed.Both the phase separation of the polyvinylpyrrolidone and polystyrene (PS) colloidal solution and the decomposition of the size-controlled PS nanobeads in the droplet played crucial roles in the formation of the unique coral-like yolk-shell structure.The CYS-NiO/C microspheres delivered a reversible discharge capacity of 991 mAh g-1 after 500 cycles at the current density of 1.0 A g-1.The discharge capacity of the CYS-NiO/C microspheres after the 1000th cycle at the current density of 2.0 A g-1 was 635 mAh g-1,and the capacity retention measured from the second cycle was 91％.The final discharge capacities of the CYS-NiO/C microspheres at the current densities of 0.5,1.5,3.0,5.0,7.0,and 10.0 A g-1 were 753,648,560,490,440,and 389 mAh g-1,respectively.The synergetic effect of the coral-like yolk-shell structure with well-defined interconnected mesopores and highly conductive carbon resulted in the excellent Li+-ion storage properties of the CYS-NiO/C microspheres.