Oxygen vacancies (OVs) dominate the physical and chemical properties of metal oxides, which play crucial roles in the various fields of applications. Density functional theory calculations show the introduction of OVs in TiO2(B) gives rise to better electrical conductivity and lower energy barrier of sodiation. Here, OVs evoked blue TiO2(B) (termed as B‐TiO2(B)) nanobelts are successfully designed upon the basis of electronically coupled conductive polymers to TiO2, which is confirmed by electron paramagnetic resonance and X‐ray photoelectron spectroscopy. The superiorities of OVs with the aid of carbon encapsulation lead to higher capacity (210.5 mAh g−1 (B‐TiO2(B)) vs 102.7 mAh g−1 (W‐TiO2(B)) at 0.5 C) and remarkable long‐term cyclability (the retention of 94.4% at a high rate of 10 C after 5000 times). In situ X‐ray diffractometer analysis spectra also confirm that an enlarged interlayer spacing stimulated by OVs is beneficial to accommodate insertion and removal of sodium ions to accelerate storage kinetics and preserve its original crystal structure. The work highlights that injecting OVs into metal oxides along with carbon coating is an effective strategy for improving capacity and cyclability performances in other metal oxide based electrochemical energy systems. Oxygen vacancies (OVs) evoked blue‐colored TiO2(B) nanobelts are first designed as superior anodes for sodium‐ion batteries. They feature remarkable high‐rate performance and durable long‐term cycle life because of their ability to take full advantage of OVs to elevate electronic conductivity and lower sodiated energy barriers. A high capacity of 80.9 mAh g−1 (at 3350 mA g−1) is still maintained after 5000 cycles.