context: In summary, a novel NVPF@5% rGO with in situ coated 3D carbon network has been successfully prepared via a two-step solid state CTR method and investigated for use as a cathode material for SIBs. The rGO carbon network architecture in NVPF@5% rGO could effectively construct ionic/electronic pathways and provide sufficient electrode–electrolyte contact area for rapid Na+/e− transport, which significantly improves the electrochemical performance of NaVPO4F. In addition, the stability of NVPF@5% rGO after long-term cycle testing was revealed by the results of the ex situ XRD and SEM analyses, which demonstrated the stable crystal structure of NaVPO4F and the sturdy construction of a robust carbon network. Furthermore, the results of the EIS, CV at various scan rates and GITT tests were implemented to study the electrode kinetic characteristics of NVPF@5% rGO. More importantly, the HC//NVPF@5% rGO full-cell system was fabricated with an HC anode and NVPF@5% rGO cathode, and exhibited superior high-rate capabilities (e.g., 81.8 mA h g−1 at 10C and 61.9 mA h g−1 at 20C) and ultralong cycling performance (82.71% capacity retention after 1500 cycles at 5C). Considering the easy synthesis route and impressive results, it is believed that this strategy can inspire the further development of high-rate and long-term cycle life electrode materials for SIBs.