An effective anode electrocatalyst in direct methanol fuel cell (DMFC) should have high activity for the oxidation of methanol and the decomposition of water, while remaining stable under the relatively harsh anode environment. Although the Pt/Ru bimetallic alloy is currently the most effective anode electrocatalyst, both Pt and Ru are expensive due to limited supplies and both are susceptible to CO poisoning. Consequently, the discovery of less expensive and more CO tolerant alternatives to the Pt/Ru catalysts would help facilitate the commercialization of DMFC. In this paper we will discuss the possibility of using tungsten carbides (WC) and Pt-modified WC as potential anode electrocatalysts in DMFC. We will provide an overview of our recent work, using a combined approach of fundamental surface science studies and in-situ electrochemical evaluation of the activity and stability of tungsten carbides. We will demonstrate the feasibility to bridge fundamental surface science studies on single crystals with the electrochemical evaluation on polycrystalline WC films. We will also discuss the synergistic effect by supporting low coverages of Pt on the WC substrate to further enhance the electrochemical performance of WC.