Direct methanol fuel cells (DMFCs) are among the most promising portable power supplies because of their unique advantages, including high energy density/mobility of liquid fuels, low working temperature, and low emission of pollutants. Various metal-based anode catalysts have been extensively studied and utilized for the essential methanol oxidation reaction (MOR) due to their superior electrocatalytic performance. At present, especially with the rapid advance of nanotechnology, enormous efforts have been exerted to further enhance the catalytic performance and minimize the use of precious metals. Constructing multicomponent metal-based nanocatalysts with precisely designed structures can achieve this goal by providing highly tunable compositional and structural characteristics, which is promising for the modification and optimization of their related electrochemical properties. The recent advances of metal-based electrocatalytic materials with rationally designed nanostructures and chemistries for MOR in DMFCs are highlighted and summarized herein. The effects of the well-defined nanoarchitectures on the improved electrochemical properties of the catalysts are illustrated. Finally, conclusive perspectives are provided on the opportunities and challenges for further refining the nanostructure of metal-based catalysts and improving electrocatalytic performance, as well as the commercial viability.