The demand for flexible, wearable electronic and electrical devices is increasing day by day. However, their application and use are limited because of the inflexible electrodes in Li-ion batteries, which are mainly used for their power sources. This work is designed to achieve high flexibility and electrical conductivity simultaneously for anode electrodes. In many cases, a carbon-based material is used as an anode and a polymer is added to increase flexibility, but this inhibits electrical conductivity. In this work, a composite of Fe₂O₃/reduced graphene oxide (rGO) and carbon nanofibers (CNFs) has been developed to enhance the flexibility and conductivity. The developed technology is based on electrospinning and thermal treatment. The 2D sheet structure of rGO is inherently very flexible, and its strong chemical bonding due to high voltage (20 kV) and continuous heat treatment makes CNFs flexible. Different amounts of iron precursor and various carbonization parameters have also been optimized to improve conductivity and capacity. An excellent reversible capacity of 1193 mAh/g at 100 mA/g with remarkable cycling-stability (989.3 mAh/g after 80 cycles) has been achieved due to the short lithium-ion diffusion length and minimal volume change during lithiation–delithiation.