Ag nanoparticles (AgNPs) (11, 15, and 25 wt.%) were deposited on the surface of the freestanding and mechanically flexible mats consisting of lignin-derived electrospun carbon nanofibers (ECNFs) by the supercritical CO2 method followed by the thermal treated at 180 degrees C. The electrochemical activity of Ag/ECNFs electrocatalyst systems towards oxygen reduction reaction (ORR) was studied in 0.1 M KOH aqueous solution using the rotating disk/rotating ring disk electrode (RDE/RRDE) technique. The SEM, TEM, and XRD results indicated that, the spherical AgNPs were uniformly distributed on the ECNF surface with sizes in the range of 2-10 nm. The electrocatalytic results revealed that, all of the Ag/ECNFs systems exhibited high activity in ORR and demonstrated close-to-theoretical four-electron pathway. In particular, the mass activity of 15 wt.% Ag/ECNFs system was the highest (119 mA mg(-1)), exceeding that of HiSPEC 4100 (TM) commercial Pt/C catalyst (98 mA mg(-1)). This study suggested that the lignin-derived ECNF mats surface-deposited with AgNPs would be promising as cost-effective and highly efficient electrocatalyst for ORR in alkaline fuel cells. (C) 2014 Elsevier Ltd. All rights reserved.