Abstract: The local distributions of the carbon structure and their changes with HTT of two kinds of C/C composites were analyzed and characterized by using laser Raman microspectroscopy. The reinforcement of the two composites is laminated carbon felt, and the matrix of the two composites consists exclusively of RL (Rough Layer) or SL (Smooth Layer) pyrolytic carbon respectively. Experimental results show the carbon crystal structure and structural change with HTT are different: not only between different elements in composite but also between different locations in the same element. The pyrolytic carbon in the carbon cloth layer with higher volume content of CF has a higher graphitization degree than the pyrolytic carbon in the mat layer. The graphitization degrees of the locations near the interface between CF and pyrolytic carbon in pyrolitic carbon or CF increase with HTT more rapidly than those far away from the interface. RL pyrolytic carbon is more graphitizable than SL pyrolytic carbon. The results indicate that it is possible to adjust and control the local distribution of carbon structure of C/C composites by means of laser Raman microspectroscopy.