This study focused on the generation of gold nanoparticles on a 4,4'-oxydiphthalic anhydride/4,4'-diamino-4 ''-hydroxytriphenylmethane-based polyimide matrix via electrospinning technique. Gold(III) chloride hydrate was used as gold precursor. The average fiber diameters of the hybrid fibers decreased up to 48% as compared with the one corresponding to the pristine polyimide fibers due to the increased Coulombic repulsions within the fibers. Gold nanoparticles were generated by thermally treating the gold salt-containing polyimde fibers. The gold nanoparticles were found to be more or less homogeneously dispersed into the polyimide fiber matrix.