The structure and electronic features of neutral and positively charged pyrene and perylene derivatives were explored. The radical cation of 1,3,6,8-tetraarylpyrene 1 was examined by ESR, UV-vis-NIR spectroscopy and theoretical calculations. The addition of 2 equiv of oxidant to 1 resulted in the formation of dication 1(2+). The single-crystal X-ray structure of 1(2+) proved that the aromatic part relocates from biphenyl unit to naphthyl unit upon 2e(-) oxidation of 1. We have also investigated the oxidation processes of 3,9-diarylperylene 2 and 3,10-diarylperylene 3. The radical cations of 2(center dot+) and 3(center dot+) showed ESR signals and the spin densities were proven to delocalize at 3,4,9,10-positions. In the case of doubly charged 3,9-diarylperylene, we could find the anthracene structure in the core, while the phenanthrene skeleton appeared in two-electron oxidized 3,10-diarylperylene. Finally we validated this phenomenon to apply for the higher analogue terrylene, discovering its large aromaticity relocation upon the 2e(-) oxidation.