This paper reports our works on the preparation of the silver-nanoparticle-incorporated ultrafine polyimide (PI) ultrafine fibers via a direct ion exchange self-metallization technique using silver ammonia complex cation ([Ag(NH(3))(2)](+)) as the silver precursor and pyromellitic dianhydride (PMDA)/4,4'-oxidianiline (4,4'-ODA) polyimide as the matrix. The polyimide precursor, poly(amic acid) (PAA), was synthesized and then electrospun into ultrafine fibers. By thermally treating the silver(I)-doped PAA ultrafine fibers, where the silver(I) ions were loaded through the ion exchange reactions of the carboxylic acid groups of the PAA macromolecules with the [Ag(NH(3))(2)](+) cations in an aqueous solution, ultrafine polyimide fibers embedded with silver nanoparticles with diameters less than 20 nm were successfully fabricated. The fiber-electrospinning process, the ion exchange process, and various factors influencing the hybrid ultrafine fibers preparation process such as the thermal treatment atmospheres and the thermal catalytic oxidative degradation effect of the reduced silver nanoparticles were discussed. The ultrafine fibers were characterized by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA).