Transition-metal selenides (TMSs) possess excellent redox reversibility and Se-rich TMSs have high theoretical specific capacity for sodium storage. Although carbon coating is a useful strategy to construct robust protective layer with additional high electronic conductivity, the formation of Se-poor TMSs inevitable results in low capacity. Herein, by simply adopting the synergistic strategy of carbonization and selenization, a novel kind of hierarchical (NiCo)Se/(NiCo)Se2@C nanostructure can be fabricated. The formation and redistribution of multiple phases can create porous structure and facilitate to expose maximum active sites, finally endowing (NiCo)Se/(NiCo)Se2@C multifunctional properties such as stable, large, fast and reversible sodium storage. The sodium-ion battery using this kind of electrode material exhibits a high initial specific capacity of 658.7 mA h g−1 at 1 A g−1, excellent rate capability of 324.9 mA h g−1 at 30 A g−1, superior cycle stability with a low capacity decay rate of 0.0046% per cycle for 1100 cycles at 20 A g−1. This work provides a facile strategy for designing unique hierarchical nanostructure for sodium-ion batteries.