The structural composition of different asphaltenes，which were separated by n⁃heptane fromVenezuelan atmospheric residue (WNAR), Liaohe vacuum residue (LHVR), Tahe atmospheric residue (THAR), Iranian vacuum residue (YLVR), and Chunliang vacuum residue (CLVR), was investigated by FT⁃IR and XPS. FT⁃IR results show that the substituents on benzene rings of asphaltenes are diverse, dominated by meta⁃disubstituted or trisubstituted benzene rings, while monosubstituted benzene rings are barely detected. Hydroxyl and sulfoxide groups existed in different asphaltenes. Oxygen⁃containing functional groups were dominated by aromatic ethers, and the aliphatic C-H structure was dominated by -CH₂ groups. XPS results indicate that surface carbon species of asphaltenes are primarily aromatic carbon with few carbon oxygen bonds, which are mostly C—O, whereas C=O and —COOH account for a very low proportion. Surface nitrogen species are mainly pyridinic nitrogen and pyrrolic nitrogen, with a small fraction of quaternary nitrogen. Surface sulfur species consist mainly of thiophenic sulfur and aliphatic sulfur. Good consistency is achieved between the two characterization results, which further verifies the accuracy of the understanding of asphaltene structural composition.