Highly porous hierarchical V2O5 cuboids have been synthesized by a template-free PVP-assisted polyxol method and the formation mechanism is studied. The cuboids are assembled from numerous mesoporous nanoplates and the preferred orientation of each single nanoplate exposes the 〈110〉 facets, facilitating lithium-ion diffusion by offering a prior channel. This material exhibits a high capacity of 143 mA h g(-1), high rate capacity of 10 C and long life cycling performance up to 1000 cycles. The excellent electrochemical performance of V2O5 cuboid electrodes is due to its unique porous cuboid morphology and optimized structural stability upon cycling. This research provides an effective route to the construction of complex porous architectures assembled from nanocrystals through a surfactant-assisted synthesis method.