Rechargeable aluminum-ion batteries (RAIBs) have attracted increasing attention owing to their high theoretical volumetric capacity, high resource abundance, and good safety performance. However, the existing RAIB systems usually exhibit relatively low specific capacities limited by the cathode materials. In this study, we developed a one-step chemical vapor deposition method to prepare single-crystal orthogonal Nb2O5 nanotubes for serving as high-performance electrode materials for RAIBs, showing a high reversible capability of 556 mA h g-1 at 25 mA g-1 and good thermal endurability at elevated temperatures (50 °C). A combination of a series of detailed ex situ structural characterization studies verified the reversible intercalation/deintercalation of chloroaluminate anions (AlCl4-) into/from the (001) planes of monocrystalline Nb2O5 nanotubes. It also revealed that the nanoarchitecture of Nb2O5 nanotubes with thin tube walls, hollow inner space and a short ion transport distance is conducive to the rapid kinetics of the insertion/extraction process. This work provides a promising route to design high-performance electrode materials based on transition metal compounds for RAIBs via the rational modulation of their structure and morphology.