TiO2 is one of the most exciting anode candidates for safe application in lithium ion batteries. However, its low intrinsic electronic conductivity limits application. In this paper, a simple sol–gel based route is presented to produce nanosize TiO2 fibers with 119 ± 27 nm diameters via electrospinning. Subsequent calcination in various atmospheres was applied to achieve anatase and anatase-rutile mixed phase crystallites with and without carbon coating. The crystallite size was 5 nm for argon calcined fibers and 13–20 nm for air calcined fibers. Argon calcined TiO2 nanofibers exhibited electronic conductivity orders of magnitude higher than those of air-calcined samples. Lithium diffusivity was increased by one time and specific capacity by 26.9% due to the enhanced conductivity. It also had a different intercalation mechanism of lithium. Hydrogen post heat-treatment was found to benefit electronic conductivity (by 3–4.5 times), lithium diffusivity (1.5–2 times) and consequently the high rate performance of the TiO2 nanofibers (over 80%). The inner mechanism and structure-property relations among these parameters were also discussed.