cis-1,4-Polyisoprene, a significant industrial elastomer, is electrospun into different nanostrucutures. Cis-1,4-polyisoprene electrospun fibers are prepared from cis-1,4-polyisoprene solutions in dichloromethane or chloroform and characterized by environmental scanning electron microscope and Fourier-transform infrared spectroscopy. ESEM observation reveals that the cis-1,4-polyisoprene fibers show a bamboo-like morphology with a nearly constant node distance, a diameter of 20-60 mu m and a length of about 300 m. In addition, within the individual nodes parallel grooves are clearly seen, which is very promising for their use in micro-printing in the field of microelectronics. Smooth cis-1,4-polyisoprene fibers with a diameter of 5-8 mu m can be obtained via electrospinning its chloroform solutions. In contrast to most polymers, the jet of cis-1,4-polyisoprene does not split during the electrospinning processes, which facilitates the collection of highly aligned fibers by using a rotating mandrel as a ground target.