This paper is an overview of the progress recently achieved in our laboratory in the development and application of four in situ methods; namely X-ray diffraction (both synchrotron-based and standard), Raman microscopy, differential electrochemical mass spectrometry (DEMS), and infrared spectroscopy. We show representative results on graphite electrodes for each method as an illustration, in particular (i) the influence of the lithium intercalation and graphite exfoliation on the shift of the (0 0 2)-reflection of graphite, (ii) Raman single point and mapping measurements of graphite surface, (iii) gas evolution during solid electrolyte interphase (SEI) formation on graphite electrodes, and (iv) the development of infrared spectra during the SEI formation in gamma-butyrolactone based electrolytes. (c) 2005 Elsevier B.V. All rights reserved.