Thermal mechanical analysis, FT- IR, WAXD and some conventional measurements, such as densities and mechanical properties, were used to characterize the effect of the modification using KMnO4 and SnCl4 on the thermal mechanical behaviors and structural changes dining the process of thermal stabilization of modified PAN precursors. to the unmodified original PAN precursors, some conclusions were drawn that the thermal stabilization starts at a lower temperature for modified PAN fibers, for example, the peak of thermal stress changes for modified PAN precursors using KMnO4 displays a decrease of 20℃ and a increase of 30% in the ultimate thermal stress, that chemical modification makes structural transformation perfect and increases by 25% of the thermal stress at the temperature range of 230℃- 300℃, that the modified PAN fibers display an increase of 100% in the thermal strain, once after pre-oxidized, show an increase of 7.8% in orientation index, and a decrease of 9.9% in crystal size for identical preload in the region of 13.1 - 14.5 MPa. It was also concluded that the modification using SnCl4 would alleviate the changes in physical and chemical stress regimes and result in improvement in structure and decrease in defects.