The discovery of the Ti₃C₂T_x compounds (MXenes) a decade ago opened new research directions and valuable opportunities for high-rate energy storage applications. The unique ability of the MXenes to host various mono- and multivalent cations and their high stability in different electrolyte environments including aqueous, organic, and ionic liquid solutions, promoted the rapid development of advanced MXene-based electrodes for a large variety of applications. Unlike the vast majority of typical intercalation compounds, the electrochemical performance of MXene electrodes is strongly influenced by the presence of co-inserted solvent molecules, which cannot be detected by conventional current/potential electrochemical measurements. Furthermore, the electrochemical insertion of ions into MXene interspaces results in strong coupling with the intercalation-induced structural, dimensional, and viscoelastic changes in the polarized MXene electrodes. To shed light on the charging mechanisms of MXene systems and their associated phenomena, the use of a large variety of real-time monitoring techniques has been proposed in recent years. This review summarizes the most essential findings related to the charging mechanism of Ti₃C₂T_x electrodes and their potential induced structural and mechanical phenomena obtained by in situ investigations.