Poor ion transport and rate capability are the main challenges for LiV3O8 as cathode material for lithium ion batteries. Here we report a novel strategy for enhancing lithium ion transport by building superionic pathways on the surface of Li0.85Na0.15V3O8 nanosheet. The two-dimensional Li0.85Na0.15V3O8 nanoparticle with an ion conductive layer of Li x V2O5 on its surface is constructed by a modified sol–gel strategy with carefully controlled sodium incorporation and elements stoichiometry. Ultrathin Li x V2O5 surface layer not only provides facile pathways for lithium migration, but also increases the structure stability during cycling. The Li x V2O5-Li0.85Na0.15V3O8 composite displays good high rate capability of 172.3mAhg−1 at 5C and excellent cycling stability of 98.9% over fifty cycles. This superior electrochemical property is attributed to the occupation of lithium site by Na+ in LiV3O8 host crystals and the surface superionic pathways of Li x V2O5 phase. Therefore, the advantages of both high ion transport and the structure stabilization in present study put forward a new strategy for achieving high-performance LiV3O8 electrode material with tailored nanoarchitecture.