Great expectation is placed on sodium ion batteries with high rate capability to satisfy multiple requirements in large-scale energy storage systems. However, the large ion radius and high mass of Na+ hamper its kinetics in case of diffusion-controlled mechanism in conventional electrode. Herein, a unique intercalation pseudocapacitance is demonstrated in low-vacancy copper hexacyanoferrate, achieving outstanding rate capability. The minimization of [Fe(CN)6] vacancy enables unhindered diffusion pathway for Na+ and little structural change during Fe2+/Fe3+ redox reaction, eliminating solid-state diffusion limits. Moreover, the Cu+ /Cu2+ couple is unexpectedly activated realizing a record capacity of copper hexacyanoferrate. A capacity of 86 mAh g-1 is obtained at 1 C, of which 50% is maintained under 100 C and 70% is achieved at 0 oC. Such intercalation pseudocapacitance might shed light on exploiting high rate electrodes among Prussian blue analogues for advanced sodium ion batteries.