Optimizing the charge and ion transport of Nb2O5 composite is great significance for developing high-performance fast charge lithium-ion batteries. We designed Nb2O5 with oxygen vacancies through a simple and cost-effective hydrothermal and high-temperature calcination treatments. Oxygen vacancies can not only improve the electronic conductivity of the composite, but also effectively provide more active sites and reduce the ion transport barrier, which improved electrochemical reaction kinetics of the Nb2O5 composite. Consequently, the synthesized Nb2O5-x microflowers delivered a specific capacity of 191.2 mA h g−1 at 1C (a retention of 94% over 200 cycles) and outstanding rate capability (103.3 mA h g−1 at 50C) for lithium storage. Significantly, this work may also broaden the pathways for designing other electrode materials with oxygen vacancies for battery systems.