To ensure optimal operation of electrochemical energy storage devices, a precise design of the interfaces formed between the electrodes and the electrolyte is essential. Si is a promising anode active material for Li-ion batteries owing to its high theoretical capacity; however, the large volume change associated with Li absorption and release hinders its practical applications. The development of high-performance storage batteries depends on the construction of an electrode-electrolyte interface that facilitates Li+ movement. To this aim, the authors have developed Si-specific interface observation methods. In this feature article, we review and discuss recent advances in the reaction behavior of Si-based anodes, particularly at the Si electrode-electrolyte interface.