<p>Single-metal phase ternary phosphorus/selenide materials have shown promise as high-capacity anodes for advanced sodium-ion batteries (SIBs) because of their substantial reversible capacity. However, their utilization has been hampered by issues such as sluggish kinetics and material pulverization during charge/discharge cycles, leading to inadequate rate capability and lifespan. To address these challenges, herein, N-doped graphene aerogel (NGA) compounding ternary FePSe₃ to form a sponge-like heterostructured architecture FePSe₃@NGA is synthesized through a combined phosphatization/selenation method and hydrothermal approach. The composite is probed as an anode for SIBs. Profiting from the enhanced electrical conduction and Na⁺ diffusion kinetics together with efficient mitigation of volume deformation, the FePSe₃@NGA presents excellent sodium storage performance. The FePSe₃@NGA delivers 302 mAh g⁻¹ after 100 cycles at 0.1 A g⁻¹, and 156 mAh g⁻¹ after 600 cycles at 1 A g⁻¹, with a capacity retention of 72%. In addition, the favorable performance of the fabricated full-cell battery (Na₃V₂(PO₄)₂F₃//FePSe₃@NGA) indicates the potential practical application of FePSe₃@NGA. The work provides insight into the furtherance of high-performance electrodes for Na⁺ storage batteries based on ternary metal phosphorus/selenide.</p>