A novel palladium catalyst immobilized on polyacrylonitrile fiber mats (Pd/PAN) was prepared by electrospinning. The catalytic activity and recyclability of the microwave-assisted Pd/PAN fiber mats were examined for the Mizoroki–Heck cross-coupling of aryl iodides with three different acrylates in aqueous solution. The morphology of the prepared Pd/PAN fiber mats was characterized by scanning electron microscopy. The large size of the PAN fiber mat-supported palladium catalyst enables much easier separation from the reaction mixture by simple filtration. Density functional theory calculation indicates that the chelation energy of palladium chloride (PdCl2) with propionitrile (model of PAN) is considerable smaller than that of PdCl2 with water, suggesting that the stability and reactivity of the Pd/PAN fiber mats catalyst could be improved through the surface derivatization with polar functional groups. Copyright © 2011 John Wiley & Sons, Ltd.