Constructing high-performance flexible lithium-ion batteries (LIBs) is imperative to satisfy the rapid demand of flexible and wearable electronics. Herein, we demonstrate a novel strategy to fabricate button-shaped amorphous Fe2O3/rGO/carbon nanofibers (am-Fe2O3/rGO/CNFs) films as freestanding flexible anodes for LIBs through in-situ electrospinning and subsequent one-step carbonization. Intercalating highly oxidized GO into the electrospun precursor not only induces tight growth of button-shaped amorphous Fe2O3 nanoparticles onto rimous CNFs matrix, but also substantially enhances the mechanical flexibility of the resulting films. Owing to the distinctive hierarchical structure, especially amorphous nature of Fe2O3 and intimate connection between am-Fe2O3 and the conducive substrate, the am-Fe2O3/rGO/CNFs-20 film delivers an excellent reversible capacity of 811 mA h g(-1 )at 0.1 A g(-1), as well as remarkable rate performance and cycling stability (584 mA h g(-1 ) over 400 cycles at a high current density of 2 A g(-1)). The electrode also exhibits impressive flexibility, which can power an array of light-emitting diodes, even bended and folded, demonstrating great potential for flexible LIBs. The facile synthesis strategy and excellent electrochemical performance endow it with great potential for application in flexible energy storage.