Utilizing convenient electrospinning techniques, CaTiO3 : Pr3+, SrAl2O4 : Eu2+, Dy3+ and CaAl2Si2O8 : Eu2+, Dy3+ nanofibers with afterglow emission were fabricated. X-ray diffraction (XRD), micro-Raman spectrometry (Raman) and scanning electron microscopy (SEM) were used to characterize the composition and morphology of electrospun nanofibers. The results showed that calcined samples were super-long nanofibers with a diameter of hundreds of nanometres. Fluorescence and afterglow properties were investigated by spectrofluorometery, which indicated that CaTiO3 : Pr3+, SrAl2O4 : Eu2+, Dy3+ and CaAl2Si2O8 : Eu2+, Dy3+ nanofibers show characteristic red, green and blue afterglow emission. The electrospun nanofibers with afterglow emissions of the three primary colors are expected to be applied in the field of miniature lighting, biological markers, multi-wavelength photo-detection, etc.