Y2Si2O7:Nd3+ nanofibers were synthesized for the first time through a combination of sol-gel and electrospinning methods. Annealing effects on the Y2Si2O7 polymorph transformation and fiber morphology were examined under a scanning electron microscope. About 901, 1061, and 1337 nm emission bands were observed in the ultrafine nanofibers, while the rough fibers with pinholes and a larger grain size exhibited only slight photoluminescence. The one-dimensional surface stress and low-temperature crystalline distortion shifted the emission bands of the Nd3+ - doped Y2Si2O7 fibers.