Electrospinning of low molecular weight compounds is relatively under-investigated compared to that of polymers. In this paper, cyclic butylene terephthalate oligomers (CBT) were fabricated into a novel fiber structure without any carrier polymer or template via melt electrospinning technique. The electrospun CBT fibers were prepared at 190 °C and characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). SEM images of the CBT fibers showed that they had a mean diameter of 1.8-2.6 μm. In contrast to most electrospun fibers, the CBT electrospun fibers were discontinuous and exhibited a rod-like morphology with an average length of 6.8-7.1 μm. This kind of morphology is rare in products made by electrospinning or electrospraying. In addition, the fiber morphology was not significantly affected by varying the preparation parameters, such as by collection distance or electric voltage value. FTIR and DSC results showed that CBT structure was not changed in the preparation process, but the degree of polymerization of CBT may be changed because of transesterification reaction. Furthermore, the formation mechanism of the discontinuous fibers was also discussed in this work.