The high capacity of SnO2 (tin oxide) and high rate capability of Li4Ti5O12 (lithium titanate, LTO) were pooled together for engineering a composite Li ion anode material in hollow fiber edifice by sol-gel/electrospinning. The electrospun porous precursor composite hollow fibers (CHFs) were heat treated either in air (SnO2/LTOA) or argon (SnO2/LTOAr) atmosphere to control grain size, porosity and presence of Ti3+ content. The morphological study performed using Field Emission Scanning Electron Microscopy and Transmission Electron Microscopy revealed smaller grain size (5–10 nm) for SnO2/LTOAr CHFs. Further, X-Ray Diffraction and X- Ray Photoelectron Spectroscopy studies illustrated a significant variation in the crystallinity and the elemental oxidation states in these CHFs respectively. Brunauer-Emmett-Teller measurements exposed the presence of high surface area and pore volume in SnO2/LTOAr CHFs. Further, the half-cell galvanostatic charge-discharge performances of SnO2/LTOAr CHFs at 1 C rate revealed a stable specific capacity of 300 mA h/g for 110 cycles with 90% capacity retention. The stable and high capacity of SnO2/LTOAr CHFs were corroborated to the presence of smaller grain size, high porosity and conductive Ti3+ providing faster lithium ion diffusion when compared to SnO2/LTOA CHFs. Electrochemical Impedance Spectroscopy study confirmed low impedances in SnO2/LTOAr CHFs due to low charge transfer and electrolyte resistances. Moreover, Li ion full-cell study performed using LiFePO4 (LFP) cathode (3 V), delivered a specific capacity of 230 mAh/g at 0.1 C rates. The excellent electrochemical performance of SnO2/LTOAr CHFs in both half-cell and full-cell modes illustrated the significance of sol-gel/electrospinning in synthesizing high performance Lithium ion batteries in a cost effective and scalable way. © 2017 Elsevier Ltd