The development of flexible electronics requires the power sources with matchable flexibility, robust mechanic property, as well as high power and energy density that would maintain the durability of flexible electronics during use. Herein, newly designed free-standing N-doped carbon films with hierarchical structure of carbon nanofibers and carbon nanotubes (CNFs/CNTs hybrids) are prepared via a simple electrospinning process. This interconnected hybrid film displays high conductivity and excellent flexibility. As a free-standing and binder-free anode material, the CNFs/CNTs hybrid electrode can achieve a reversible capacity of 1099.5 mAh g(-1) at a current density of 0.05 A g(-1) with superior rate capabilities and excellent cyclic stability. What's more, utilizing the CNFs/CNTs hybrid film as the electrode, this assembled highly flexible half and full batteries also show attractive performances and can easily light up a group of 12 light emission diodes at flat and various bending positions, making it possible to be applied in the flexible electronic devices.