Strontium-doped samarium cobaltite (Sm0.5Sr0.5CoO3-delta, SSC) fibers were successfully fabricated by electrospinning of a precursor gel derived from polyvinyl alcohol (PVA) and aqueous metal nitrate. After calcination of the as-spun SSC fibers in microwave furnace at above 500 degrees C, SSC fibers of 100 +/- 20 nm in diameter with well-developed cubic-perovskite structure were successfully obtained. The crystal structure morphology, and grain structure of the fibers were influenced by the calcination temperature and the grain structure was evolved to "bamboo" structuredpolycrystalline SSC at above 700 degrees C.