It is indispensable to develop and design high capacity, high rate performance, long cycling life, and low‐cost electrodes materials for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Herein, MoO2/MoS2/C, with dual heterogeneous interfaces, is designed to induce a built‐in electric field, which has been proved by experiments and theoretical calculation can accelerate electrochemical reaction kinetics and generate interfacial interactions to strengthen structural stability. The carbon foam serves as a conductive frame to assist the movement of electrons/ions, as well as forms heterogeneous interfaces with MoO2/MoS2 through CS and CO bonds, maintaining structural integrity and enhancing electronic transport. Thanks to these unique characteristics, the MoO2/MoS2/C renders a significantly enhanced electrochemical performance (324 mAh g−1 at 1 A g−1 after 1000 cycles for SIB and 500 mAh g−1 at 1 A g−1 after 500 cycles for LIBs). The current work presents a simple, useful and cost‐effective route to design high‐quality electrodes via interfacial engineering.