An economical route based on electrospinning and layer-by-layer (LBL) self-assembly processes has been developed to synthesize unique MoO2-modified TiO2 nanofibers, comprising a core of TiO2 nanofibers and a thin metal-like MoO2 nanolayer. The thickness of the MoO2 nanolayer can be tuned by altering the precursor concentration or the LBL cycles. When evaluated for their lithium-storage properties, the MoO2-modified TiO2 nanofibers exhibit a high discharge capacity of 514.5 mA h g(-1) at 0.2 C over 50 cycles and excellent rate capability, demonstrating that enhanced physical and/or chemical properties can be achieved through proper surface modification.