In this work, an economical route based on hydrothermal and layer-by-layer (LBL) self-assembly processes has been developed to synthesize unique Al2O3-modified LiV3O8 nanosheets, comprising a core of LiV3O8 nanosheets and a thin Al2O3 nanolayer. The thickness of the Al2O3 nanolayer can be tuned by altering the LBL cycles. When evaluated for their lithium-storage properties, the 1 LBL Al2O3-modified LiV3O8 nanosheets exhibit a high discharge capacity of 191 mA h g−1 at 300 mA g−1 (1C) over 200 cycles and excellent rate capability, demonstrating that enhanced physical and/or chemical properties can be achieved through proper surface modification.