We report the preparation of polymer nanofibers with enhanced flame retardancy by coaxial electrospinning polyamide 66 (PA 66) and nanoscale graphene hybridized with red phosphorus (NG-RP). Transmission electron microscopy and energy-dispersive X-ray spectroscopy revealed that the nanofibers contained a NG-RP-based core surrounded by a PA 66 shell. The flame-retardant characteristics of the nanofibers were investigated by thermal gravimetric analysis, micro combustion calorimetry, and a series of vertical flame tests. The encapsulation of the NG-RP not only enhanced the flame-retardant characteristics of the nanofibers, but also improved their mechanical properties while maintaining the color and luster of the polymer, making the resultant nanofibers appropriate for use in a wide range of applications.