[en] Highlights: • ZIF-67 derived core/shell structured [email protected] polyhedrons anchored 3D RGO, are used as binder-free anode for SIBs. • The unique [email protected] binder-free anode exhibits an outstanding cycling stability and a high rate capability. • The excellent properties can be attributed to synergistic effects between core/shell [email protected] polyhedrons and RGO networks. • The present strategy for [email protected] architectures can be extended to other novel electrode materials. A novel strategy is developed to synthesize metal-organic framework (MOF) derived core/shell structured [email protected] polyhedrons anchored on 3D reduced grapheme oxide (RGO) on nickel foam (NF) as binder-free anode for high performance sodium-ion battery, through an in-situ low-temperature phosphidation process from ZIF-67 derived core/shell [email protected] polyhedral structures. The unique [email protected] binder-free anode exhibits a remarkable electrochemical performance with outstanding cycling stability and high rate capability, delivering a specific capacity of 473.1 mA h g⁻¹ at a current density of 100 mA g⁻¹ after 100 cycles. The excellent properties can be attributed to synergistic effects between core/shell [email protected] polyhedrons and RGO networks. The unique core/shell [email protected] polyhedrons can offer more electrode/electrolyte contact area and reduce the diffusion distance of Na⁺, while carbon layer shell can enhance electronic conductivity and buffer volume change, and prevent CoP from pulverization and aggregation. Furthermore, 3D RGO networks can provide adequate surface areas for a high loading content of CoP and enhance charge transfer kinetics. Meanwhile, RGO/NF can efficiently act as a binder and electrical conductor to interconnect the separate [email protected] polyhedrons. The present strategy for [email protected] architectures can be extended to other novel electrodes for high performance energy storage devices.