With the aim of establishing a data simultaneous comparison, the Principal Component Analysis (PCA) statistical tool was applied to LiNi0.6Mn0.2Co0.2O2/graphite Li-ion cells electrolyte's decomposition products detected by UHPLC-ESI-HRMS. Herein, we illustrate how the chemometric tool associated with mass spectrometry data can be relevant to provide information about the presence of unusual molecules. Indeed, pristine Triton X-100 surfactant molecules used in the electrode elaboration process were detected after the impregnation stage. However, as they chemically react and oxidize at a potential lower than 4.5 V vs Li/Li+, only surfactant derivatives and classical ageing molecules were observed, respectively, after storage and cycling stages at 55 degrees C, leading to a triangle-type correlation circle. On the other hand, global schemes of LiPF6-based electrolyte degradation pathways were elaborated from a comparative study with literature to help interpret results in future electrolyte ageing studies.