In this work, the Cu-alginate/graphene aerogels were prepared by using alginate, graphene and copper chloride as precursors by a freeze-drying process. Finally, N-doped carbon aerogels supported by Cu nanoparticles (NPs) (Cu/N-CAs) were obtained through annealing in the NH3 atmosphere. The morphology, microstructures, specific surface area, and pore size distribution were studied by SEM, XRD, and BET analysis. The results showed that a significant amount of Cu NPs were uniformly disseminated on the aerogels’ surface, and the catalysts’ specific surface area reached 141 m2/g. Electrochemical tests revealed good catalytic capabilities for the oxygen reduction reaction (ORR) of the as-obtained Cu/N-CAs. Compared to the commercial 20%Pt/C, the Cu/N-CAs exhibited comparable catalytic performance, superior catalytic stability and methanol resistance. The transfer of 3.94 electrons indicated that the Cu/N-CAs were undergoing a four-electron (4e-) ORR process.