The article presents comprehensive studies of the chemical composition and morphology of nanotubular anodic TiO2 layers at the first stages of the porous structure nucleation, by scanning electron microscopy (SEM), Auger spectroscopy (AES), time-of-flight secondary ion mass spectrometry (TOF.SIMS). Our goal was to show the profile distribution of chemical elements and reaction products at each of the initial stages of the anodic oxide growth in the ethylene glycol-based electrolyte containing fluoride, which will help expand the understanding of pore formation mechanism.