Membrane electrode assembly (MEA) is the key component of direct methanol fuel cell (DMFC), the structure and its preparation methods may bring great effects on the cell performances. Due to the requirement of the high performance of the MEA for the micro direct methanol fuel cell (DMFC), we provide a novel double-catalyst layer MEA using CCM-GDE (Catalyst Coated Membrane，CCM；Gas Diffusion Electrode，GDE) fabrication method. The double-catalyst layer is formed with an inner catalyst layer (in anode side: PtRu black as catalyst, in cathode side: Pt black as catalyst) and an outer catalyst layer (in anode side: PtRu/C as catalyst, in cathode side: Pt/C as catalyst). The fabrication procedures are important to the new structured MEA, thus three kinds of fabrication methods are studied, including CCM-GDE, GDE-Membrane and CCM-GDL methods. It was found that the CCM-GDE technology may enhance the contact properties between the catalyst and PEM, and increase the electrode reaction areas, resulted in increasing the performance of the DMFC.