Constructing hollow architectures based on metal sulfides is of great interest for high-performance electrode materials for sodium-ion batteries because of their intriguing properties and various applications. However, the relatively low volumetric density and high fragile structure are the obstacles blocking the development of hollow-structured electrode materials. In this work, ball-in-ball structured (Ni0.33Co0.67)9S8@C nanospheres have been synthesized by using NiCo-glycerate as the precursor via solvothermal reaction, which was followed by a carbon coating treatment. In this structural design, hollow cavities are generated between the inner and outer balls to effectively accommodate the volume changes of the metal sulfides in the processes of charging/discharging, whereas the uniform carbon coating can increase the electrical conductivity and maintain the structural stability during repeated cycling. The Rietveld refinement, in situ X-ray diffraction, and ex situ X-ray photoelectron spectroscopy analyses provide evidence for an enlarged lattice parameter, weaker Co-S and Ni-S bondings, and a synergistic effect in (Ni0.33Co0.67)9S8@C toward boosting the conversion reaction and reversible formation of sulfur in the fully charged state, with sulfur trapped within the composite to additionally account for the superior cycling stability of this material. Capacitive behavior has been verified to dominate the electrochemical reaction, enabling fast charge-transport kinetics. Impressively, the double structural protection combined with the free hollow space and complete carbon layer endows the (Ni0.33Co0.67)9S8@C nanospheres with good electrochemical performance, featuring high cyclability and good rate capability.