The activity of PtCu/C catalysts in methanol electrooxidation is studied in HClO4 solution. The electrochemical behavior of catalysts is compared for samples in the “as obtained” state and after their pretreatment in nitric acid which decreases the copper content in their composition. It is found that the partial selective dissolution of the alloying component renders no negative effect on the behavior of bimetallic catalysts. The prepared materials exhibit the high tolerance toward intermediates of methanol oxidation and their specific activity exceeds by a factor of 5–7 the activity of the commercial Pt/C catalysts. The results of this study open up the possibility of using de-alloyed platinum-copper catalysts in alcohol fuel cells, because this considerably decreases the risk of contamination of the polymeric membrane.