In the present research, the modified Perdew–Wang exchange and correlation (MPW1PW91) quantum chemical method was applied to determine the impact of external electric field on the total energy, dipole moment, the energies of frontier orbitals, HOMO–LUMO gaps, and aromaticity of the Cr(CO)3(η6-C6H6) complex. Percentage compositions of frontier orbitals have been calculated in terms of the specific groups in the absence and presence of external electric field. Moreover, variation of the global reactivity descriptors was examined in response to changes in the electric field. The nucleus independent chemical shift (NICS) values have been used to assess the aromaticity of the complex.