Rich reserves, lower price, and high theoretical capacity of FeS₂ as a promising anode for SIBs can’t cover up its low Na⁺ diffusion kinetic and severe volume expansion. Herein, the core-shelled hollow sphere FeS₂ (CHS-FeS₂) was synthesized using modified MIL-88B(Fe) as templates to promote Na⁺ diffusion kinetic and release volume expansion. In the preparation process of MIL-88B(Fe), the citric acid participated in coordination with Fe³⁺ to adjust the concentration of Fe³⁺ and regulate MIL-88B(Fe) curvature, thus constructing MIL-88B(Fe) with different nanostructures. After calcination, the Fe₂O₃ with different nanostructures was achieved due to the different combustion rates of MIL-88B(Fe) catalyzed by Fe³⁺ and different diffusion amounts of Fe³⁺ to the surface of MIL-88B(Fe). The FeS₂ with different nanostructures were formed after sulfuration. Especially, the uniform sphere-like MIL-88B(Fe) with suited Fe³⁺ concentration was achieved when the citric acid was 0.05 g, leading to the formation of CHS-FeS₂ after calcination and sulfuration. Additionally, as the electrode for SIBs in a half-cell system, the CHS-FeS₂ exhibited a high specific capacity of 617.5 mAh/g at 0.5 A/g, maintained 546.5 mAh/g after 100 cycles, and still 224 mAh/g was retained at a current density of 20 A/g. Furthermore, the full cell of CHS-FeS₂//NVP@C achieved a high specific capacity of 279.3 mAh/g at 0.05 A/g, a specific capacity of 156.7 mAh/g at 1.0 A/g, and 87.8 % of initial capacity after 100 cycles at 0.1 A/g, reflecting the excellent cycling stability and rate capability. We believe this paper provides an inspiration for constructing hollow structural materials with rich reserves, lower prices, excellent cycling stability, and rate performance.