We report the preparation of poly(2,5-dicyclohexylphenylene-1,4-ethynylene) (PDE)/poly(ethylene oxide) (PEO) hybrid nanofibers by electrospinning technique. The hybrid nanofibers were characterized by a host of characterization techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, atomic force microscopy, optical and scanning electron microscopy. The results showed a successful preparation of PDE/PEO composite nanofibers. The diameter of the hybrid nanofibers ranges between 500 and 1000 nm. The results showed that this kind of hybrid nanofibers could be a possible candidate in color display devices.