Eu(2+)-doped Ca(Sr)Al(2)Si(2)O(8) nanofibers with an average diameter of 500 nm were in situ synthesized by electrospinning and calcination in reduced ambience. X-ray diffraction results confirmed that the Ca(Sr)Al(2)Si(2)O(8):Eu(2+) nanofibers were of the anorthite phase. An intense blue emission due to the 4f(6)5d(1) -> 4f(7) transition of Eu(2+) ions was observed in the nanofibers. The emission band shifted to the blue region with the substitution of Ca by Sr due to the change in the crystal field surrounding Eu(2+) ions. The long afterglow decay curves of Ca(Sr)Al(2)Si(2)O(8):Eu(2+) nanofibers contain rapid (similar to 13.86 s) and slow (similar to 157.12 s) components. By the co-doping of Dy(3+) ions, the emission and long afterglow duration of nanofibers were improved remarkably. These Ca(Sr)Al(2)Si(2)O(8):Eu(2+), Dy(3+) electrospun nanofibers with excellent emission and long afterglow properties were potentially applied in biological marker, display, sensor, etc. (C) 2009 The Electrochemical Society. [DOI:10.1149/1.3223986] All rights reserved.