A novel composite anode catalyst layer for direct methanol fuel cell is reported in this paper. The dual-layer anode, which is based on the catalyst coated membrane technique, characterizes a morphological variety of the catalyst layer. The inner sub-layer with a dense morphology can effectively suppress methanol crossover. On the other hand, the outer sub-layer modified by the pore-forming agent, NH 4 HCO 3 and the carbon nanotubes can enhance the electrochemical surface area and increase the catalyst utilization. The structural improvement of anode catalyst layer results in a 40% increment in maximum power density during the single cell test at 30°C.