Nickel-based materials have been extensively deemed as promising anodes for sodium-ion batteries (SIBs) owing to their superior capacity. Unfortunately, the rational design of electrodes as well as long-term cycling performance remains a thorny challenge due to the huge irreversible volume change during the charge/discharge process. Herein, the heterostructured ultrafine nickel sulfide/nickel phosphide (NiS/Ni2P) nanoparticles closely attached to the interconnected porous carbon sheets (NiS/Ni2P@C) are designed by facile hydrothermal and annealing methods. The NiS/Ni2P heterostructure promotes ion/electron transport, thus accelerating the electrochemical reaction kinetics benefited from the built-in electric field effect. Moreover, the interconnected porous carbon sheets offer rapid electron migration and excellent electronic conductivity, while releasing the volume variance during Na+ intercalation and deintercalation, guaranteeing superior structural stability. As expected, the NiS/Ni2P@C electrode exhibits a high reversible specific capacity of 344 mAh g−1 at 0.1 A g−1 and great rate stability. Significantly, the implementation of NiS/Ni2P@C//Na3(VPO4)2F3 SIB full cell configuration exhibits relatively satisfactory cycle performance, which suggests its widely practical application. This research will develop an effective method for constructing heterostructured hybrids for electrochemical energy storage.