Vitrinite, the main maceral of humic coals, has complicated structure. And it’s not easy to study the vitrinite structure using single method. So different kind of pyrolysis methods have been used for the purpose to reveal the structure of vitrinites. The result shows that the composition of adsorbed hydrocarbon is controlled by the type and maturity of vitrinites. Pyrolysates of telocollinite are mainly composed of aromatics while that of desmocollinite is mainly composed of aliphatics. And it shows that the ratio of aromatics in pyrolysate raises with maturity.