In this study, we evaluated the activity of binary PtMn/C, ternary PtMnX/C (X = Fe, Co, Ni, Cu, Mo and, Sn) and quaternary PtMnCuX/C (X = Fe, Co, Ni, and Sn) and PtMnMoX/C (X = Fe, Co, Ni, Cu and Sn) alloy catalysts towards the oxygen reduction reaction (ORR) in acidic solution. Although all catalysts exhibited improved activities towards the ORR if normalized by the mass of Pt; when they are considered per milligram of total metal only a handful of them illustrated improved activities towards the ORR in terms of onset potential and current intensity determined by cyclic voltammetry with respect to pure Pt/C. PtMnCu/C, PtMnCuFe/C and PtMnMoCu/C were found to be the best catalysts for ORR. In order to gain a better understanding of the pathways of ORR, Pt/C, PtMnCu/C, PtMnCuFe/C and PtMnMoCu/C were further studied using a Rotating Disk Electrode (RDE) and Rotating Ring Disk Electrode (RRDE). Tafel plots and Koutecky-Levich analysis of the data revealed that the activity towards the ORR is better with PtMnMoCu/C followed by PtMnCuFe/C and PtMnCu/C. The estimated average number of the electrons transferred during the ORR process was found to be around 4e(-). The average percentage of the generated H2O2 reached as high as similar to 7.5% with PtMnMoCu/C. All these data point to the fact that the pathways of ORR which produce H2O2 and H2O as final products took place. As a final comparison for this series of catalysts, this study also gives a better selection of the catalysts that may preferably be used at the anode for ethanol oxidation or at the cathode for ORR to yield fuel cells with substantial output voltages. (C) 2013 Elsevier B.V. All rights reserved.