In recent research, electrospun nanofibers (NFs) from polymer solutions containing metal salts were used to produce high-temperature superconducting ceramic (HTSC) NFs through pyrolysis. In this research, the production of phase separated nanostructures inside NFs spun from polymer solutions containing metal salts was investigated. The metal salts were expected to be preferentially driven into one of the phases (the amorphous phase in a semi-crystalline polymer and the more hydrophilic phase in a triblock copolymer) and yield nanostructured ceramics upon pyrolysis. Surprisingly, the electrospun NFs exhibited the spontaneous formation of a core-sheath structure. The metal-atom-rich core exhibited a 10 nm scale structure while no such structure was observed in the metal-atom-poor sheath. Both the repulsion of metal atoms by the positive surface charge and the exclusion of the metal atoms from the crystallizing front that moves inward from the surface were shown to contribute to the spontaneous formation of the core-sheath structure. (c) 2011 Elsevier Ltd. All rights reserved.