Materials for lithium‐ion batteries (LIBs) with excellent electrochemical performance are of significance to meet the increasing demand for rechargeable batteries. Niobium pentoxide (Nb2O5), as an intercalation material with promising electrochemical properties has caught our attention. In this study, Nb2O5 nanoparticles were successfully synthesized through a classical sol‐gel process. The nanoparticles with a size of less than 5 nm were uniformly coated on carbon materials, i. e., reduced graphene oxide (rGO) and three‐dimensionally ordered macroporous (3DOM) carbon, under the same proportion, to explore which kind of carbon materials is more suitable to improve the electrochemical performance of Nb2O5 as an anode for LIBs. Nb2O5/3DOM carbon composite exhibited a superior electrochemical performance to the other two materials, where a high reversible capacity of 519 mA h g−1 could be maintained at the current density of 5.0C (C=201.7 mA g−1). Furthermore, the specific capacity of Nb2O5/3DOM carbon composite maintained 1163 mA h g−1 at the current density of 0.2C (C=201.7 mA g−1) after 100 cycles.