The first and second order Raman spectra of graphite during the first lithiation and delithiation have been investigated in a typical lithium-ion battery electrolyte. In situ, real-time Raman measurements under potential control enable the probing of the graphitic negative electrode surface region during ion insertion and extraction. The experimental results reveal the staging formation of a single particle within a free standing graphitic electrode. In particular, the in situ behaviour of the double resonance 2D band during the lithiation and delithiation of graphitic carbon has not been previously reported. The 2D band was observed to shift from 2681 to 2611 cm−1 and the band shape transformed into a single Lorentzian from 0.24 to 0.15 V vs. Li/Li+, providing further information on the electronic structure and C–C bonding of stage 3 and 4 graphite intercalation compounds. The behaviour of the 2D band is in keeping with the Daumas–Hérold model of electrochemically derived intercalation, where the graphene layers are flexible and deform around domains of intercalating lithium ions.