Direct methanol fuel cells (DMFCs) are promising for use in portable devices because of advantages such as high fuel energy density, low working temperature and low emission of pollutants. Nanotechnology has been used to improve the performance of DMFCs. Catalytic materials composed of small, metallic particles with unique nanostructure supparted on carbons or metal oxides have been widely investigated for use in DMFCs. Despite our increased understanding of this type of fuel cell, many challenges still remain. This paper reviews the current developments of nanostructured elec- trocatalytic materials and porous electrodes for use in DMFCs. In particular, this review focuses on the synthesis and characterization of nanostructured catalysts and supporting materials. Both computational and experimental approaches to optimize mass transportation in porous electrodes of DMFCs, such as theoretical modeling of internal transfer processes and preparation of functional structures in membrane electrode assemblies, are introduced.