Polyacrylonitrile (PAN) and PAN/-cyclodextrin (-CD) microspheres were prepared via an electrospinning method. The PAN microspheres could be successfully obtained in a suitable range of concentrations of electrospun PAN solutions. When -CD was added to the PAN solutions, electrospun PAN/-CD composite spheres were prepared. The morphology of the spheres was characterized by scanning electron microscopy (SEM); it showed that the spheres had uniform diameter and a smooth surface. The composition of the composite microspheres was studied by Fourier transform infrared spectroscopy (FTIR). The results showed that the -CD was incorporated in the polymer microspheres.