Asphaltenes generated by a multiple precipitation procedure were found to contain n-alkanes from C14 to C31, which show an odd over even preference. This result further indicates that alkyl chains or alkylene bridges appear mostly as substituents in the coal macromolecular network. Comparison of the elemental analysis and surface area of pyrolysis chars shows that the surface areas correlate well with the heteroatom content of chars and that of the original coals as well. However, the gasification reactivity in carbon dioxide of ash-free chars cannot be interpreted in terms of their surface area. During the pyrolysis of asphaltenes, chars were formed via the mesophase route. The polarized light optical microscopy of chars confirmed that fluidity of the carbonization system is a major factor controlling the optical texture of resultant chars. Pyrolysis of asphaltenes showed that most of the gaseous components are formed by the cleavage of weak bonds like aryl-alkyl-ethers and strong bonds, mainly methylene and biarylether bridges between the aromatic moieties and methyl groups on the aromatic rings in asphaltene structure.