Composites of Ag-incorporated carbon nanofibers (CNFs) confined with Fe2O3 nanoparticles (Ag–Fe2O3/CNFs) have been synthesized through an electrospinning method and evaluated as anodes for lithium batteries (LIBs). The obtained Ag–Fe2O3/CNF anodes show good LIB performance with a capacity of 630 mAh g−1 tested at 800 mA g−1 after 150 cycles with almost no capacity loss and superb rate performance. The obtained properties for Ag–Fe2O3/CNF anodes are much better than Fe2O3/CNF anodes without Ag-incorporating. In addition, the low-temperature LIB performances for Ag–Fe2O3/CNF anodes have been investigated for revealing the enhanced mechanism of Ag-incorporating. The superior electrochemical performances of the Ag–Fe2O3/CNFs are associated with a synergistic effect of the CNF matrix and the highly conducting Ag incorporating. This unique configuration not only facilitates electron conduction especially at a relative temperature, but also maintains the structural integrity of active materials. Meanwhile, the related analysis of the AC impedance spectroscopy and the corresponding hypothesis for DC impedance confirm that such configuration can effectively enhance the charge-transfer efficiency and the lithium diffusion coefficient. Therefore, CNF-supported coupled with Ag incorporating synthesis supplied a promising route to obtain Fe2O3 based anodes with high-performance LIBs especially at low temperature.