Crystalline Cu3Pt nanoparticles supported on graphitized carbon are synthesized by using a modified sol–gel method, and subsequent thermal annealing leads to alloying of Pt with Cu and formation of a partially ordered Pmm structure. Electrochemical dealloying under potentiodynamic conditions (potential cycling) induces not only changes from rather spherical high-index faceted to more cuboctahedral low-index faceted core–shell structures for particles in a size range of 10–20 nm but also percolation for some particles larger than 20 nm. In contrast, during dealloying under potentiostatic conditions (potential hold) the semispherical shape of small particles is completely retained and extensive porosity is formed on all particles larger than 20 nm. Other degradation processes are not observed on performing an additional accelerated aging test; hence, the high specific and mass activity of the catalyst decreases only slightly, mainly owing to continuing Cu leaching. The difference in dealloying protocols and their effect on the structure of the catalysts as well as their activities, considering the promising porosity formation, are discussed and indicate future directions for a rational design of active and stable oxygen reduction reaction catalysts.