The major aim of this work was to synthesize thio-stabilized CdTe nanoparticles(NPs) in an aqueous solution, which was then enwrapped with cetyltrimethylammonium bromide(CTAB), and finally transferred to the polyvinylpyrrolidone(PVP) matrix by electrospinning. The PVP nanofibers containing CdTe NPs were characterized by scanning electron microscopy(SEM) and transmission electron microscopy(TEM), to observe the morphology of the nanofibers and the distribution of CdTe NPs. The selective area electronic diffraction(SAED) pattern verified that CdTe NPs were cubic lattice. The photoluminescence(PL) spectrum indicated that CdTe NPs existed in an optical style in PVP nanofibers. Moreover, X-ray photoelectron spectra(XPS) revealed that thiol-stabilized CdTe NPs were enwrapped by CTAB, and PVP acted as a dispersant in the process of electrospinning.