Acrylonitrile-butadiene-styrene (ABS) is a polymer composing of acrylonitrile, butadiene, and styrene. It has been widely used in industry because of its good mechanical and physical properties. The fabrication of ABS fibers, however, has been rarely studied. Here the fabrication of ABS fibers has been reported by an electrospinning technique, in which the sizes and morphologies of the fibers can be controlled by adjusting the electrospinning conditions. The morphologies of the ABS fibers can also be transformed by annealing the fibers on poly (methyl methacrylate) (PMMA) films. After annealing, the ABS fibers gradually transform to ABS particles embedded in the PMMA films by a mechanism similar to the Rayleigh-instability-type transformation. To extend the applications of the electrospun ABS fibers, electroless deposition of copper is also conducted, resulting in copper-coated ABS fibers.