The direct methanol fuel cell (DMFC) is among the most promising alternative energy sources for the near future owing to its advantages of simple construction, compact design, high energy density, and relatively high energy-conversion efficiency. Typically, the electrodes in DMFC is comprised of a Pt-based catalysts supported on great potential of carbon materials such as multi-walled carbon nanotubes (MWCNTs), carbon black (CB), graphene, etc. It is desired to develop an electrode with high surface area, good electrical conductivity and suitable porosity to allow good reactant flux and high stability in the fuel cell environment. This chapter will provide recent advances in Pt-based binary and ternary electrocatalysts on carbon supports for high-performance anodes in DMFC. Through studying the effects of composition-, support-, and shape dependent electrocatalysts, further fundamental understanding and mechanism in the development of anode catalysts for DMFC will be provided in details.