A novel composite with antimony (Sb) nanoparticles anchored in three-dimensional carbon network (denoted as SbNPs@3D-C) is successfully synthesized via a NaCl template-assisted self-assembly strategy, followed by freeze-drying and one-step in-situ carbonization. The three-dimensional interconnected macroporous carbon framework can not only stabilize the architecture and buffer the volume expansion for Sb nanoparticles, but also provide high electrical conductivity for the whole electrode. Consequently, as a sodium-ion battery anode, the SbNPs@3D-C delivers a high reversible capacity (456 mAh g−1 at 100 mA g−1), stable cycling performance (94.3% capacity retention after 500 cycles at 100 mA g−1) as well as superior rate capability (270 mAh g−1 at 2000 mA g−1). When compared with commercial Sb particles, the SbNPs@3D-C exhibits dramatically enhanced electrochemical performance. Free from expensive template sources and complex manipulation, this work might shed some light on the synthesis of low-cost and high-performance materials for the next “beyond lithium” battery generation.