Ultrathin 2D materials can offer promising opportunities for exploring advanced energy storage systems, with satisfactory electrochemical performance. Engineering atomic interfaces by stacking 2D crystals holds huge potential for tuning material properties at the atomic level, owing to the strong layer-layer interactions, enabling unprecedented physical properties. In this work, atomically thin Bi2MoO6 sheets are acquired that exhibit remarkable high-rate cycling performance in Li-ion batteries, which can be ascribed to the interlayer coupling effect, as well as the 2D configuration and intrinsic structural stability. The unbalanced charge distribution occurs within the crystal and induces built-in electric fields, significantly boosting lithium ion transfer dynamics, while the extra charge transport channels generated on the open surfaces further promote charge transport. The in situ synchrotron X-ray powder diffraction results confirm the material's excellent structural stability. This work provides some insights for designing high-performance electrode materials for energy storage by manipulating the interface interaction and electronic structure.