AbstractThe feasibility of transition metal carbides (TMCs) as promising high‐rate electrodes is still hindered by low specific capacity and sluggish charge transfer kinetics. Improving charge transport kinetics motivates research toward directions that would rely on heterostructures. In particular, heterocomposing with carbon‐rich TMCs is highly promising for enhancing Li storage. However, due to limited synthesis methods to prepare carbon‐rich TMCs, understanding the interfacial interaction effect on the high‐rate performance of TMCs is often neglected. In this work, a novel strategy is proposed to construct a binary carbide heteroelectrode, i.e. incorporating the carbon‐rich TMC (M=Mo) with its metal‐rich TMC nanowires (nws) via an ingenious in situ disproportionation reaction. Results show that the as‐prepared MoC‐Mo2C‐heteronanowires (hnws) electrode could fully recover its capacity after high‐rates testing, and also possesses better lithium accommodation performance. Kinetic analysis verified that both electron and ion transfer in MoC‐Mo2C‐hnws are superior to those of its singular counterparts. Such improvements suggest that by taking utilization of the interfacial component interactions of stoichiometry tunable heterocarbides, the electrochemical performance, especially high‐rate capability of carbides, could be significantly enhanced.