Porous preoxidated polyacrylonitrile (PAN) fiber mats, which was prepared by electrospinning and then followed by thermal treatment, has been used for the immobilization of copper catalyst. FT-IR/ATR spectra and XRD pattern show that the linear polymer structure of the PAN fiber mat can be converted into the ladder molecular structure at the high temperature. The morphology of the copper catalyst supported on the preoxidated PAN fiber mats was examined by scanning electron microscopy (SEM). The catalytic activity and stability of the fiber mat supported copper catalyst have been evaluated using the Mizoroki-Heck cross-coupling reaction of aryl iodides with different acrylates. It was found that the catalytic activities of fiber mat supported copper catalyst could be significantly promoted by addition of small amount of additives, such as ethylene glycol. (C) 2013 Elsevier B.V. All rights reserved.