The manufacturing process can modify the micromechanical structure, usefulness, and functionality of foams. Although one-step foaming is a simple process, controlling the morphology of the foams is difficult compared to the two-step processing method. In this study, we investigated the experimental differences in thermal and mechanical properties, particularly combustion behavior, between PET−PEN copolymers prepared by the two methods. With an increase in foaming temperature T f , the PET−PEN copolymers became more fragile, and the breaking stress of the one-step PET− PEN foamed at the highest T f was only 2.4% of that of the raw material. For the pristine PET−PEN, 24% of the mass was burned, leaving 76% as a molten sphere residue. The two-step MEG PET− PEN had only 1% of its mass remaining as a residue, whereas the onestep PET−PENs had between 41 and 55%. The actual mass burning rates were similar for all the samples except the raw material. The coefficient of thermal expansion of the one-step PET−PEN was about two orders of magnitude lower than that of the two-step SEG.