Despite its importance in dictating electrochemical reversibility and cell chemistry kinetics, the solid electrolyte interphase (SEI) on graphitic anodes remains the least understood component in Li ion batteries due to its trace presence, delicate chemical nature, heterogeneity in morphology, elusive formation mechanism, and lack of reliable in situ quantitative tools to characterize it. This work summarizes our systematic approach to understand SEI live formation, via in situ electrochemical atomic force microscopy, which provides topographic images and quantitative information about the structure, hierarchy, and thickness of interphases as function of electrolyte composition. Complemented by an ex situ chemical analysis, a comprehensive and dynamic picture of interphase formation during the first lithiation cycle of the graphitic anode is described. This combined approach provides an in situ and quantitative tool to conduct quality control of formed interphases.