Chinese rice ball-like hollow nitride spheres with a high specific surface area and excellent conductivity have been successfully fabricated via a hydrothermal method. Polyaniline is assembled onto the surface of these nitride spheres. Benefiting from the synergistic effect of the hollow structure, high conductivity, abundant active sites, sturdy microstructure, and additional pseudocapacitance provided by the polyaniline, the prepared CRBHNS-PANI electrode presents ideal electrochemical properties and good cycling stability for supercapacitors according to electrochemical tests. The nanocomposite exhibits a high specific capacitance of 530.8 F g⁻¹ at a current density of 0.5 A g⁻¹ and excellent rate capability (retains 80.4% even at a current density of 5 A g⁻¹). Moreover, the material also has good cycling stability, with 87.4% performance retention after 1000 cycles at a current density of 5 A g⁻¹. This study demonstrates that the performance of PANI-based supercapacitors can be greatly enhanced by limited assembly around novel transition metal nitrides with a unique microscopic morphology and structure.