7Li MAS NMR, usually a bulk characterization technique, is used here to analyze the positive electrode/electrolyte interphase. The sharpening of the NMR spectra line shape as the amount of surface species increases shows that the observed signal is clearly the sum of signals due to the distribution of lithium ions in the interphase in terms of distance from the bulk of electrode active material. This technique is then used to compare characteristics of the interphase coming from the contact with LiPF6-based electrolyte in the case of storage or electrochemical cycling. A clear influence of the change of potential on the interphase configuration and in particular on its intimacy with the bulk of active material is deduced from the change in NMR spectra lineshape. This information is hardly obtained by other characterization technique, making NMR a powerful tool for the study of interphases and passivation layers in lithium batteries materials.