One-dimensional high-quality CdS/poly(ethylene oxide) (PEO) hybrid nanoparticle-polymer fibers were fabricated by an electrospinning method, followed by self-assemble technologies with co-fed H2S atmosphere at 60 degrees C. The structural and spectral information of the resulting hybrid nanofibers was characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffractometer. The diameters of CdS/PEO hybrid nanofibers ranged from 90 to 200 nm and the average dimension of CdS nanoparticle within fibers from 4 to 12 nm. An interesting aspect of the CdS/PEO nanofibers shown in photoluminescence spectra and fluorescence images is that the fluorescence peaks of CdS/PEO were shifted along with changing the mass ratio of CdS/Poly(ethylene oxide), and consequently the size and phase of nanocrystal CdS.