Considerable interest in utilizing methanol oxidation reaction in fuel cells has recently spurred a new wave of research to develop novel catalysts to drive this reaction. The main problem has been to diminish the ubiquitous poisoning effects inadvertently associated with Pt which is the main active component of most catalysts. In this work, we have investigated bifunctional metal catalysts, including PtRu, PtPd, PtAu, and PtFe, deposited on novel nanostructured substrate materials, such as the semiconducting transition metal oxides (WO_3-x, TiO_2-x, etc.), in hopes of modifying the catalyst properties and providing new mechanistic paths for removal of CO poisoning intermediate. Special attention has been paid to surface diffusion of adsorbed CO and weak interactions of methanol with catalysts. The investigations were performed using AFM, EQCN, and point defect formation voltammetry. Various nanostructural and compositional options for enhancement of electrocatalytic effects in methanol oxidation reaction have been considered and they are discussed in details.