We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.