Commercializing fuel cells requires inexpensive devices that will operate reliably over a wide range of power demands. Both of these requirements necessitate that active, stable, and cost effective electrocatalysts be developed to not only replace the expensive noble metals now used in alkaline fuel cell electrodes, but also reduce the requisite catalyst loading where the pertinent reactions of interest are O2 reduction and H2 oxidation. Much of the recent activity in both electrolysis and fuel cell technologies have centered on either proton exchange membrane (PEMFC/SPEWE) or in solid oxide electrolytes (SOFC/SOEC) because of the potential for high current/power densities and efficient packing. In spite of the great progress, PEM based technologies still suffer from the inherent cost penalty of using precious metals and the cost and stability of the membrane and its long term reliability. Similarly, SOFC/SOEC technologies have been slow in bringing down the operating temperature due to electrode/electrolyte restraints. In this work, alkaline fuel cells are investigated with the goal of enhancing cathode catalytic performance by studying and comparing a polycrystalline silver-manganese alloy system and a nanostructured silver-manganese system. The silver-manganese system was chosen as both silver and manganese dioxide show similar oxygen reduction catalytic activities to platinum in an alkaline electrolyte. The novel silver-manganese alloy was produced by compressing powders of the two pure metals, then arc-melting in a vacuum atmosphere. Compressed pure manganese powder was held separately in the chamber and melted first, to remove any residual oxygen and to eliminate any oxidation products forming in the silver-manganese alloy. The electrochemical behaviour of pure silver and three silver-manganese alloys (5, 10 and 15 wt% manganese in bulk silver) were examined in 0.1 M KOH at 80°C to assess their relative performance in relation to the oxygen reduction reaction (ORR). From the observed linear voltammograms, the ORR initiated at approximately the same potential for all samples, however the maximum current density for the silver-manganese alloy samples showed a significant increase over that observed for pure silver. Nanocatalyst systems of silver and silver with manganese dioxide were also electrolessly deposited onto carbon nanofibers (CNFs) and their structure, composition and morphology were studied by STEM imaging and EDX. Manganese dioxide deposits as a thin layer covering the entire carbon nano-fiber surface, while silver deposits as distinct nano particles on top of the manganese dioxide layer. In the absence of manganese, silver deposits directly on to the carbon nanofibers. Silver deposits typically demonstrate Volmer-Weber type growth as relatively spherical or columnar structures with particle sizes ranging from 15-125 nm and an average size of approximately 40 nm on both pure carbon and manganese dioxide surfaces. Fabrication of electrodes consisting of the active area of CNFs and catalyst, polytetrafluoroethylene and a thin nickel mesh were completed by a rolling, pressing and heating procedure. Electrodes consisting of pure silver on CNFs, manganese dioxide on CNFs and silver with manganese dioxide on CNFs were electrochemically investigated and CNFs loaded with 10 wt% silver showed the highest activity towards the oxygen reduction reaction.