The carbon fibrous mats with high conductivity (50 S cm(-1)) formed by carbon nanofibers with an average diameter of similar to 150 nm have been fabricated by thermally treating the electrospun polyacrylonitrile fibers. The platinum clusters are electrodeposited on the carbon nanofibrous mats (CFMs) by multi-cycle CV method. In contrast to the catalytic peak current of methanol oxidation on commercial catalyst (185 mA mg(-1) Pt), the catalytic peak current on optimum Pt/CFM electrode reaches to similar to 420 mA mg(-1) Pt despite of the large size (50-200 nm) of the Pt clusters, revealing that the special structure of carbon fibrous mats is favorable to improve the performance of catalyst. (c) 2008 Elsevier B.V. All rights reserved.