Aniline oligomers have been intensively studied in the past years. in particular, aniline oligomers substituted with electron-donor groups have been synthesized and its electronic properties calculated. However, when an electron-acceptor group is attached to the benzenoid ring of the oligoaniline, strong effects over its electronic properties an expected to happen. In this work some semiempirical quantum chemistry calculations of geometric structures, and energy level distribution of aniline and substituted anilines and its corresponding oligomer are presented. Geometry calculations of aniline and oligoanilines have been performed by using the PM3 and AM1 methods. Energy calculations and W-vis spectra have been done by using the ZINDO/S-CI method. The studied substituents are methoxy, methyl, fluorine, nitro, and cyano groups, located at positions 2 or 3, in the benzenoid ring. This series of substituent groups involves a large range of sigma-pi electron-donor-acceptor capability. The methoxy and the nitro substituted tetranilines show an interaction between the oxygen of the substitutent and the nitrogen of the oligomer through an hydrogen atom. These hydrogen bonds modify largely the structure of the oligomers. Particularly nitro groups show the strongest electrostatic attraction between hydrogen and oxygen. The cyano and the nitro groups (sigma-pi acceptor) induce an increasing of the ionization potential. Theoretical analysis of the orbital energies of molecules substituted with electron-acceptor groups shows a lowering of the LUMO energy values larger than those in the HOMOs cases. A decreasing of the energy of the first optical transition when the electron acceptor capability of the substituent increases is shown. Tetranilines substituted with nitro groups display a band around 380 nm in the calculated W-vis spectrum. Thus, oligoanilines substituted with electron-acceptor groups (especially nitro groups) show the lowest energy gap and they are the most encouraging material for semiconducting applications that we have studied.