AbstractZinc borates have merits of low voltage polarization and suitable redox potential, but usually suffer from low rate capability and poor cycling life, as an emerging anode candidate for Na+storage. Here, a new intercalator‐guided synthesis strategy is reported to simultaneously improve rate capability and stabilize cycling life of N, B co‐doped carbon/zinc borates (CBZG). The strategy relies on a uniform dispersion of precursors and simultaneously stimulated combustion activation and solid‐state reactions capable of scalable preparation. The Na+storage mechanism of CBZG is studied: 1) ex situ XRD and XPS demonstrate two‐step reaction sequence of Na+storage: Zn6O(OH)(BO3)3+Na++e−↔3ZnO+Zn3B2O6+NaBO2+0.5H2①, Zn3B2O6+6Na++6e−↔3Zn+3Na2O+B2O3②; reaction ① is irreversible in ether‐based electrolyte while reversible in ester‐based electrolyte. 2) Electrochemical kinetics reveal that ether‐based electrolyte possesses faster Na+storage than ester‐based electrolyte. The composite demonstrates an excellent capacity of 437.4 mAh g−1in a half‐cell, together with application potential in full cells (discharge capacity of 440.1 mAh g−1and stable cycle performance of 2000 cycles at 5 A g−1). These studies will undoubtedly provide an avenue for developing novel synthetic methods of carbon‐based borates and give new insights into the mechanism of Na+storage in ether‐based electrolyte for the desirable sodium storage.