The Solid Electrolyte Interphase (SEI) is a nanoscale thickness passivation layer that forms as a product of electrolyte decomposition through a combination of chemical and electrochemical reactions in the cell and evolves over time with charge/discharge cycling. The formation and stability of SEI directly determine the fundamental properties of the battery such as first coulombic efficiency (FCE), energy/power density, storage life, cycle life, and safety. The dynamic nature of SEI along with the presence of spatially inhomogeneous organic and inorganic components in SEI encompassing crystalline, amorphous, and polymeric nature distributed across the electrolyte to the electrolyte‐electrode interface, highlights the need for advanced in situ/operando techniques to understand the formation and structure of these materials in creating a stable interface in real‐world operating conditions. This perspective discusses the recent developments in interface‐sensitive in situ/operando techniques, providing valuable insights and addressing the challenges of understanding the composition/structure/property of SEI and their correlations during the formation processes at spatio‐temporal resolution across various length scales.