In this study, carbon aerogel (CA) substrates were prepared by using bacterial cellulose as template, then flexible W-O-C/CA and WC/CA composite electrode materials were prepared by impregnation and high temperature treatment. The effects of preparation process on the phase, morphology and electrocatalytic performance of methanol were investigated. With the increase of heat treatment temperature and the extension of holding time, the phase change occur as tungsten precursor→tungsten oxide (WO3, WO3-x, WO2)→W→WCx→WC. For the flexible electrode prepared at 700 ℃ for 2 h, the phases of the supported particles are oxygen-deficient tungsten oxide (WO3-x) ,WO2 and tungsten carbide (WC). The electrode has good electrocatalytic performance for methanol oxidation (peak current density of 76.5 mA cm-2 at 0.8 V) and long-term cycling stability, the peak current density remains 88% of the initial value after 1000 cycles. This flexible electrode is expected to be used in the anode of portable or micro methanol fuel cell.