The silver nanocrystals (AgNCs) anchored on graphene oxide (GO) catalysts have been synthesized by a facile chemical reduction and nontemplate method using ascorbic acid (AA) as reducing agent and have successfully employed as a cathode catalyst for oxygen reduction reaction (ORR) in direct alkaline fuel cells (DAFCs). The morphological characterizations demonstrate that the AgNCs have crystalline form and grafted onto reduced graphene oxide (AgNCs/rGO_AA). Comparatively better dispersion and higher population of AgNCs have observed on AA treated AgNCs/rGO than NaBH 4 which is known as conventional reducing agent. The electrochemical catalysis in 0.1 M KOH electrolyte has demonstrated that the AgNCs/rGO_AA has an excellent electrocatalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 40% higher mass activity with large specific activity against 20 wt% Pt/C with faster electron transfer rate per O 2 . Moreover, the reaction kinetic parameters have confirmed that the ORR at AgNCs/rGO_AA catalyst not only follows a 4e -process with lowering H 2 O 2 formation but also proceeds on with good stability and fuel selectivity in DAFCs. The oxygen reduction reaction (ORR) is an interesting research area and already attracted widespread attention of researches from all over the world because of its important role in the application of energy storage and conversion devices, such as fuel cells (FCs) and metal−air batteries in alkaline media.1-4 Due to superior energy conversion efficiency and potential for providing clean energy, FCs are in the main attention as next generation energy sources. 5,6 As the FCs consists of anode and cathode electrodes, the greatest effect on the performance of FCs is the oxidation/reduction reaction kinetics occurring at the respective electrodes. Unfortunately, the sluggish kinetic rate of ORR at the cathode is the main obligation to be applied in industry. 6 Typically, the platinum (Pt) and/or Pt-based materials are known as the most efficient electrocatalyst in the cathode for ORR catalysis [7][8][9][10] but unfortunately, the Pt-based materials have faced many troubles such as its susceptibility to time dependent drift and CO poisoning, 11,12 slow electron-transfer kinetics, 13 high costs, limited supply, 14 and poor durability. 15 For those reasons, Pt has hindered the widespread commercialization of FCs technology. To overcome the cost challenges, significant efforts have focused on the development of alternative non-Pt catalysts that are based on mainly non-precious metals and/or various heteroatom-doped carbonaceous materials. [16][17][18] Among the non-Pt metal catalysts studied, silver (Ag)-based carbon nanomaterials have been explored as promising candidates with higher activity and stability in alkaline medium recently. [19][20][21][22] According to previous reports, the Ag is an ideal alternative of Pt because it is not only abundantly available in nature and much cheaper but also higher electrical and thermal conductive than Pt....