The relationship between the microstructure, mechanical properties, and oxidation behavior of pitch-, polyacrylonitrile (PAN)-, and Rayon-based carbon fibers (CFs) has been studied in detail. Three types of carbon fiber were exposed to isothermal oxidation in air and the weight change was measured by thermogravimetric analyzer (TGA) apparatus. After activation energy was gained according to the conversion at reacting temperature, the value of specific surface area and the surface morphology was compared, and the reaction mechanism of oxidation affecting development of pores of carbon fibers was examined. This study will lead to a new insight into the relationship between the microstructure and mechanical properties of carbon fibers.