Nanofibers of poly(acrylonitrile)/Eu3+ were prepared by using sol-gel processing and electrospinning technique. The diameter of the nanofibers in the non-woven membranes was about 70-100 nm. The nanofibers were characterized by scanning electron microscopy (SEM), fourier transform infrared (FT-IR). and photoluminescence (PL). In our work, the PAN/Eu3+ hybrid nanofibers showed excellent photoluminescence properties. A possible PL mechanism was proposed accordingly. It is expected that these kind of materials would be applied in equipments such as optoelectronic nanodevices in the future. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.