Hollandite Ag2Mn8O16 was prepared by solid-state chemical method, and was used as an electrochemical catalyst for oxygen reduction in lithium-air batteries. Several techniques including X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to evaluate the characteristics of Ag2Mn8O16 catalyst and composite air electrodes made with Ag2Mn8O16/single-wall carbon nanotube (SWNT)/carbon nanofiber (CNF). The catalytic effect of Ag2Mn8O16 catalyst was studied using galvanostatic discharge method. Li-air cell with Ag2Mn8O16 catalyst exhibits a reduced discharge overvoltage and a large discharge capacity. This work shows that the hollandite Ag2Mn8O16 material is an effective electrochemical catalyst to enhance the electrochemical performance of lithium-air batteries. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.085203jes] All rights reserved.