The demonstration to apply the combinatorial method using a repeated cyclic voltammetry is reported to find the anodic material for DMFC that shows a higher electrocatalytic activity and that can replace a portion of precious metals with cheap ones. The activity of newly found electrocatalyst whose composition was determined through high-throughput screening was compared with that of commercially available Johnson-Matthey Pt(50)Ru(50). It was found Pt(77)Ru(17)Mo(4)W(2) was more active and stable than Pt(50)Ru(50) in methanol electro-oxidation. The repeated cyclic voltammetry makes the combinatorial method expand into a screening tool to find the electrocatalyst that not only showing an initial excellent performance but also being active in the long-run reaction.