An electrolyte-probe screening method was proposed for combinatorial electrochemical analysis, which is not only suitable for half-cell but also for full-cell electrochemical research. The accuracy of this method was examined by investigating the electrochemical oxidation of methanol in an electrode array for various methanol∣air cells. Reproducible voltage–current curves were obtained for various parallel experiments in the same electrode array. The effects of catalyst loading and methanol concentration on the discharge performance for the methanol∣air cells were observed by fast screening the anode electrodes in the array containing different catalyst loadings and various methanol concentrations, respectively.