Improving the catalytic activity of Pt-based bimetallic nanoparticles is a key challenge in the application of proton-exchange membrane fuel cells. Electrochemical dealloying represents a powerful approach for tuning the surface structure and morphology of these catalyst nanoparticles. We present a comprehensive study of using electrochemical dealloying methods to control the morphology of ordered Cu₃Pt/C intermetallic nanoparticles, which could dramatically affect their electrocatalytic activity for the oxygen reduction reaction (ORR). Depending on the electrochemical dealloying conditions, the nanoparticles with Pt-rich core–shell or porous structures were formed. We further demonstrate that the core–shell and porous morphologies can be combined to achieve the highest ORR activity. This strategy provides new guidelines for optimizing nanoparticles synthesis and improving electrocatalytic activity.