In this study, silver was electrochemically deposited onto glassy carbon (GC) substrate using constant potential regime and tested for oxygen reduction reaction (ORR) in alkaline media. The surface morphology of Ag/GC electrodes was studied by scanning electron microscopy (SEM). It was established that after 10 s of deposition, a number of Ag nanoparticles with the size of 15 nm are produced that grow to about 45 nm after 300 s of electrodeposition. The ORR studies were conducted in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. The Tafel slope at low current densities for electrodeposited silver is in the range from −70 to −80 mV. The RDE measurements showed that the electron transfer number (n) is 3.5 for smaller amounts of electrodeposited Ag, and it increases with increasing the loading of Ag on the GC surface. These n values suggest that the electroreduction of oxygen on Ag/GC electrodes proceeds mainly to water.