Polyacrylonitrile nanofibrous mats coated with continuous thin gold films (Au-PAN) have been fabricated by combining the electrospinning and electroless plating techniques. The Pt particles are electrodeposited on the Au-PAN fibers surface by multi-cycle CV method, and the Au-PAN decorated with Pt (Pt/Au-PAN) shows higher activity toward methanol electro-oxidation. The catalytic peak current for methanol oxidation on the optimum Pt/Au-PAN electrode can reach about 450 mA mg -1 Pt which is much larger than the catalytic peak current for methanol oxidation (118.4 mA mg -1 Pt) on the electrode prepared by loading commercial Pt/C on Au-PAN (Pt/C/Au-PAN). Further experiments reveal that the Pt/Au-PAN electrodes exhibit better stability and smaller charge transfer resistance than Pt/C/Au-PAN electrodes, which indicates that the Au-PAN may be developed as supporting material for catalyst. The microscopy images of the electrodes show that the Pt particles deposited on Au-PAN conglomerate into larger particles, and that the Pt/C catalyst loaded on the Au-PAN also exhibits conglomeration after stability test. The hydrogen adsorption-desorption experiments indicate that the electrochemical surface area of the Pt particles for the both kinds of electrodes has decreased after stability test.