The presence of internal rotation in sigma bonds is essential for conformational analysis of organic molecules and its understanding is of great relevance in chemistry, as well as in several other areas. However, for aromatic compounds that have substituent groups, withdrawers or donors of electron, there are no data in the literature to explain their rotational barriers. In this context, the work studied the internal rotational barriers of electron donating and withdrawing groups in aromatic compounds using the MP3, MP4, and CCSD(T) methods and the influence of substituents' nature on barrier heights was investigated through calculations based on the theory of Natural Bond Orbitals (NBO) and Quantum Theory of Atoms in Molecules (QTAIM). The results obtained showed that the CCSD(T) method is the one that best describes the internal rotational barriers, followed by MP4 and MP3 and the electron donating groups decrease the barrier, whereas electron withdrawing groups increase. Through the NBO analysis it was possible to observe that for withdrawing groups the interaction of the molecular orbitals is more accentuated promoting the increase of the rotational barrier of these compounds. Through the QTAIM analysis it was possible to show that, for electron donating groups, the internal rotation is influenced by the loss of electronic density when the substituents is perpendicular to the ring plane, however, for withdrawing groups the density is little influenced, regardless of the two conformations (minimum and maximum energy). Two molecules showed free rotation, trichloromethylbenzene and methylbenzene, and the theoretical calculations NBO and QTAIM showed that for these species there is no difference in the properties studied when there is rotation of the dihedral angle.