Coal undergoes a series of complex physical and chemical changes during pyrolysis. These changes have something to do with coal structure. In this paper, the features and kinetics of five kinds coal pyrolysis were investigated, respectively, by a TGA system in a stream of Nitrogen and Argon with a heating rate of 20 K/min up to 1173 K. The chemical structures of these coals were examined by the FT-IR technique, and their microcrystalline structure was measured by the XRD technique. The results showed that the pyrolysis of five coals consists of three stages; the second stage is the strongest pyrolysis stage. The characteristic temperature T-0.05 and T-0.5 are different for five coals and are affected by their chemical structure, microcrystalline structure parameter, volatile matter (V-d) content, and environmental atmosphere. The pyrolysis active energy E and preexponential factor A in the second reaction stage have a compensation effect, and they are affected by coal structure and reaction atmosphere.