A novel in situ microscopic approach combining Raman and infrared micro-spectroscopy for the study of interfacial reactions and the spectral characterization of the local structure at the same spot on the surface of electrodes was developed. As a proof of concept, the impact of vinylene carbonate and ethylene sulfite additives on SEI film formation was studied, using highly reflective glassy carbon (GC) as a model system for graphite-based anodes. By micro-FTIR spectroscopy, solvation–desolvation interfacial phenomena were detected, while the carbonaceous material was characterized by micro-Raman spectroscopy at the same spot on the GC surface.