The poor conductivity of anodic carbon materials at low temperature hampers their high-level applications in Li ion batteries (LIBs). Introducing some reliable metals with good electrical conductivity into anodes could alleviate these problems. In this work, the novel composites of Fe-added Fe3C carbon nanofibers (Fe/Fe3CCNFs) were synthesized via facile electrospinning method and used as anode materials for LIBs. The resulting anodes with Fe/Fe3CCNF materials exhibited a high reversible capacity of 500mAhg−1 tested at 200mAg−1 even after 70 cycles and excellent performance at room temperature. Importantly, it delivered a high capacity of 250mAhg−1 at 400mAg−1 even after 55 cycles at a low temperature of −15°C. The superior low-temperature electrochemical performance of the Fe/Fe3CCNF anodes is associated with an improved effect of the highly conducting Fe at low temperature.