Nanostructured binary skutterudites represented by MX3 are potential thermoelectric materials for high efficiency thermoelectric. In this work, we synthesized for the first-time high purity nanofibers of CoSb3 and rare earth filled LaCo4Sb12 with external diameters < 100 nm via electrospinning which provides a simple, easy to implement and versatile technique to develop novel nanostructured-based thermoelectric materials.