Nanocrystalline cellulose (NCC) can be converted into carbon materials for the fabrication of lithium-ion batteries (LIBs) as well as serve as a substrate for the incorporation of transition metal oxides (TMOs) to restrain the volume expansion, one of the most significant challenges of TMO-based LIBs. To improve the electrochemical performance and enhance the longer cycling stability of LIBs, a nanocrystalline cellulose-supported iron oxide (Fe2O3) composite (denoted as NCC–Fe2O3) is synthesized and utilized as electrodes in LIBs. The obtained NCC–Fe2O3 electrode exhibited stable cycling performance, better capacity, and high-rate capacity, and delivered a specific discharge capacity of 576.70 mAh g−1 at 100 mA g−1 after 1000 cycles. Moreover, the NCC–Fe2O3 electrode was restored and showed an upward trend of capacity after working at high current densities, indicating the fabricated composite is a promising approach to designing next-generation high-energy density lithium-ion batteries.