Carbon/carbon composites were prepared with phenol-formaldehyde resin, one kind of commercial carbon fiber, and a stabilized fiber that was developed in our laboratory. The effect of pyrolysis on the microstructure, fracture behavior, and flexural strength of the composites during the carbonization process was studied. During the pyrolysis of the composites a chemical reaction at the fiber/resin interface apparently took place. A thermogravimetry (TG) study indicated that the use of stabilized fiber reinforced composites inhibited decomposition reactions and thermal fragmentation in the matrix resin, and reduced the weight loss of the final composites. The X-ray reflection of the resin and the two composites showed a reflection appearing at 2 theta almost-equal-to 12-degrees when the samples were carbonized above 600-degrees-C. The intensity of this reflection in the composites made with stabilized fiber was higher than that of the composite made with carbon fiber. Because of the formation of strong bonding in the fiber-matrix interface, the composites made with stabilized fiber showed catastrophic failure and low flexural strength below carbonization temperatures of 600-degrees-C. Above 600-degrees-C, the flexural strength of the composites increased with an increase in the carbonization temperatures, even if the fracture behaviors showed catastrophic failure. The flexural strength of the composites made with carbon fiber showed pseudo-plastic patterns and debonding with very little fiber pullout. Above 800-degrees-C, these composites showed a catastrophic failure and smooth failure surfaces. During pyrolysis the flexural strength decreased with an increase in the carbonization temperature.