The thermal degradation of chitin biomass with various molecular structures was investigated by thermogravimetric analysis (TG), and the gaseous products were analyzed by connected mass spectroscopy (MS). The chemical structure and morphology of char residues collected at 750°C using the model substrates GlcNH2 and GlcNAc, were characterized systematically. The experimental results disclosed that one main mass loss stage was observed for each substrate. Chitosan samples with high molecular weight shown the more thermal stability, and chitin showed the highest thermal stability. Additionally, it was found that catalysts play a significant role during the pyrolysis. The gaseous evolution components, including NH3, H2O, CO, and CO2 were observed by on line MS. The experimental results disclosed that the obtained carbonaceous materials had lost the original hydrocarbon structure totally, and transformed into an aromatic structure with high carbon and nitrogen content, which was identified by XPS and solid state NMR.