Transition metal phosphides (CoP, etc.), featuring rich natural abundance and remarkable theoretical capacity, suffer from extremely poor rate capability and severe energy decay for sodium storage due to their huge volume change and low electronic conductivity. Herein, an elaborate hierarchical superstructure, nitrogen-doped carbon wrapped CoP in-situ anchored on Ti₃C₂T MXene (CoP@NC/Ti₃C₂T), was fabricated by crosslinking ZIF-67 on Ti₃C₂T flakes followed by successive carbonization and phosphorization. In principle, the dual modification for CoP nanoparticles through NC coating and Ti₃C₂T support can dramatically accelerate the ionic/electronic transportation and alleviate the structure change upon repeated sodiation/desodiation, thus leading to superior electrode integrity, modified ohmic polarization, and excellent electrochemical reversibility. Consequently, the elaborated hierarchical superstructure delivers impressive sodium storage performances with large capacity (396.06 mA·h/g at 0.1 A/g up to 100 cycles), robust rate performance (237.8 mA·h/g at 2.0 A/g), and satisfied cyclability (capacity retention of 81.3% at 1.0 A/g after 1,200 cycles). In principle, systematic electrochemical and characterizations measurements manifest that the high pseudocapacitive effect to charge storage, enhanced ionic diffusion kinetics, and remarkable electrochemical reversibility contribute to the impressive sodium storage performance of target CoP@NC/Ti₃C₂T. Importantly, the unique modification strategy reported in this study paves a way to fabricate high-performance electrode for SIBs.