Polyacrylonitrile (PAN) was often used as a composite fiber matrix due to its good spinning characteristics. Herein, photoluminescent quantum dot-doped nanofibers with tunable diameters were successfully prepared using electrospinning by adding CdSe/CdS quantum dots (QDs) in PAN spinning solution. The morphology and structure of CdSe/CdS-PAN nanofibers were characterized by scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR), and the mechanical and photoluminescent properties of CdSe/CdS-PAN nanofibers were investigated. Stable photoluminescent nanofibers were obtained owning to the improved stability of photoluminescent property of CdSe/CdS QDs in the PAN nanofiber. The stable photoluminescent CdSe/CdS-PAN nanofibers might be used for anti-fake labels, ultraviolet sensors, smart textiles and optoelectronic devices.