Direct methanol fuel cell (DMFC) is considered to be a promising commercial energy conversion device for portable electronics due to its many advantages. In order to improve the performance of DMFC, many companies and research institutes have been launching the deep research and obtaining a lot of conspicuous achievements. In this paper, the electrocatalytic mechanism and porous electrode mass transfer process in membrane electrode assembly (MEA) are analyzed. In addition, combined with the preparation process of MEA, multilayer ordered structures and internal transfer process of the cell, recent progresses of MEA in DMFC are discussed.