The CdS/PVP fibers have been successfully prepared by electrospinning. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Vis absorption spectra were used to characterize the structure. Results showed that the concentration of polymer solutions and the CdS amount in the solvent influenced the morphology and the diameter of the electrospun fibers. The electrospinning from CdS/PVP in ethanol produced a structure having a combination of fibers, ribbons, beads and an unexpected half hollow sphere (HHS) structure. When the weight ratio of CdS:PVP was kept at 1:1000, the morphologies of electrospun products changed from HHS, to beaded fibers and ribbons, to beaded fibers, and to bead-free fibers with the increasing of the PVP concentration.