Based on the favorable ionic conductivity and structural stability, sodium superionic conductor (NASICON) materials especially utilizing multivalent redox reaction of vanadium are one of the most promising cathodes in sodium‐ion batteries (SIBs). To further boost their application in large‐scale energy storage production, a rational strategy is to tailor vanadium with earth‐abundant and cheap elements (such as Fe, Mn), reducing the cost and toxicity of vanadium‐based NASICON materials. Here, the Na3.05V1.03Fe0.97(PO4)3 (NVFP) is synthesized with highly conductive Ketjen Black (KB) by ball‐milling assisted sol‐gel method. The pearl‐like KB branch chains encircle the NVFP (p‐NVFP), the segregated particles possess promoted overall conductivity, balanced charge, and modulated crystal structure during electrochemical progress. The p‐NVFP obtains significantly enhanced ion diffusion ability and low volume change (2.99%). Meanwhile, it delivers a durable cycling performance (87.7% capacity retention over 5000 cycles at 5 C) in half cells. Surprisingly, the full cells of p‐NVFP reveal a remarkable capability of 84.9 mAh g−1 at 20 C with good cycling performance (capacity decay rate is 0.016% per cycle at 2 C). The structure modulation of the p‐NVFP provides a rational design on the superiority of others to be put into practice. Ketjen Black (KB) branch chains encircle the Na3.05V1.03Fe0.97(PO4)3 (NVFP) like wearing “pearl,” making the segregated particles link to access the overall conductivity and activating the unusual structural distortion of FeO6 in NVFP during electrochemical progress, thus stimulating plenty of Na+ de/intercalation at plateau region with reversible phase transition and acquiring a favorable rate performance and durable cycling lifespan under fine volume variation.