Sodium-ion batteries (SIBs) have attracted considerable attention for large-scale energy storage systems as a promising alternative to lithium-ion batteries (LIBs) due to the huge availability and low-cost. Yet the development of SIBs has been hindered by the low reversibility, sluggish ion diffusion, as well as large volume variations. Herein, we report an efficient hydrothermal method for fabricating hierarchical porous Na3V2(PO4)3/C (NVP/C) microspheres assembled from interconnected nanoflakes. The NVP nanocrystals are uniformly wrapped by N-doped carbon layer. As a half-cell cathode, the NVP/C porous microspheres exhibit superior rate capability (99.3 mA h g−1 at 100 C) and excellent cyclic stability (79.1% capacity retention over 10,000 cycles at 20 C). A full-cell configuration coupled with NVP/C cathode and SnS/C fibers anode exhibits an estimated practical energy density of 223 W h kg−1. The superior performance can be ascribed to the hierarchical porous micro/nano structure along with N-doped carbon encapsulation, which provide bicontinuous electron/ion pathways, large electrode-electrolyte contact area, as well as robust structural integrity. This work provides a promising approach for boosting the electrochemical performance of battery materials via the integration of hierarchical structure and heteroatoms doped carbon coating.