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A combined wide angle X-ray diffraction (WAXD)/small-angle X-ray scattering (SAXS)/scanning electron microscopy (SEM)/density study of structure and morphology was carried out for a large series of pyromellitic dianhydride-oxydianiline (PMDA-ODA) polyimide (PI) samples processed using different powder metallurgy techniques. Using a combined DSC/creep rate spectroscopy (CRS)/long-term creep resistance (LTCR) approach, their molecular dynamics, thermal and elastic properties, and creep resistance in the temperature range from 20 to 4708C were also studied. Both a choice of the method of formation of fine PI particles and the order of applying high pressure relative to high temperature to form the monolithic samples led to the observation of significant property differences. Relationships between the processing conditions, structure, and properties were determined. As a result, the conditions for optimizing certain PMDA-ODA polyimide properties, especially creep resistance and elastic properties at extreme temperatures, were determined.