The storage of electrical energy at high charge and discharge rates is an important technology in modern society, and can enable electric vehicles, supply back-up for solar and wind energy, and firm the output of a renewables-based grid. In this work, highly porous Li4Ti5O12/C nanofibers are successfully designed and prepared through electrospinning combined with a post-two-step annealing process. Such a unique Li4Ti5O12/C hybrid with a well-defined porous nanoarchitecture exhibits ultrahigh cycling rates and superior cycling stability, when evaluated as an anode material for both lithium ion batteries and supercapacitors. This work presents a facile and cost-effective approach that is potentially competitive for scaling-up production of high-performance electrode materials for high-rate electrochemical energy-storage devices.