Theoretical models and ab initio Hartree-Fock wavefunctions have been used to investigate the S(2p) core level binding energies (BE), of pyrolized S-containing, carbonaceous materials. Comparison between experimental and calculated data for thiophene permits the accuracy of the present approach to be established. A systematic study of different situations demonstrates that, in these materials, non-oxidized S atoms can show peaks at very high BE relative to the C(ls) peak at 285.0 eV. This study confirms that the peak at 164.1 eV corresponds to ＇thiophenic＇ S atoms. On the other hand, it shows that the peaks at higher BE could correspond to S atoms replacing C atoms in three-coordinated structures of graphene layers, in agreement with the arguments suggested in the experimental works. The energetic similarity between the two peaks at very high BE makes it difficult to differentiate between them, although the results of the present study seem to suggest that the peak at experimental BE approximate to 166 eV could correspond to S atoms coordinated to two C and one H atoms at the edge of graphene layers, while the peak at approximate to 169 eV would correspond to S atoms replacing C atoms in inner positions of the graphene layers, and it is bonded to three C atoms.