Some of the recent topics on the use of microelectrodes for the materials characterization, especially for the materials in battery and sensor applications, were overviewed. Results were presented for conducting polymers and for battery active materials such as a graphitized carbon. The filament-type and the interdigitated-array-type microelectrodes were prepared, and used respectively for the particle-level characterization and for the in situ conductivity measurement. It is demonstrated that the microelectrode-based characterization techniques bring unique information, which will contribute to the design of high performance micro devices.