In situ monitoring the evolution of electrode materials in micro/nano scale is crucial to understand the intrinsic mechanism of rechargeable batteries. Here a novel on‐chip Langmuir–Blodgett nanowire (LBNW) microdevice is designed based on aligned and assembled MnO2 nanowire quasimonolayer films for directly probing Zn‐ion batteries (ZIBs) in real‐time. With an interdigital device configuration, a splendid Ohmic contact between MnO2 LBNWs and pyrolytic carbon current collector is demonstrated here, enabling a small polarization voltage. In addition, this work reveals, for the first time, that the conductance of MnO2 LBNWs monotonically increases/decreases when the ZIBs are charged/discharged. Multistep phase transition is mainly responsible for the mechanism of the ZIBs, as evidenced by combined high‐resolution transmission electron microscopy and in situ Raman spectroscopy. This work provides a new and adaptable platform for microchip‐based in situ simultaneous electrochemical and physical detection of batteries, which would promote the fundamental and practical research of nanowire electrode materials in energy storage applications.