Ag4Sn/C catalyst is synthesized by a solution phase reduction method assisted with ultrasonic at 0 °C. The as-prepared catalyst is characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical measurements. The Ag4Sn intermetallic electrocatalyst displays enhanced electrocatalytic activity towards oxygen reduction reaction (ORR) and good methanol-tolerant property in alkaline media. The ORR catalyzed by Ag4Sn/C proceeds a four-electron pathway. The obtained results are important for the development of Ag-based catalysts in alkaline fuel cells.