Doping carbon materials with Fe and N attracts great attention due to its promising application in preparing ORR electrode with high performance and low cost. Previously, Fe, N-codoped catalyst (Fe/N/C) had been synthesized via a simple one-pot method using carbon materials, dopamine and FeCl3 by our group. However, the unstable activity and low selectivity (electron transfer number of similar to 3.5) are key problems that should be solved. Herein, trace sulfur has been introduced into Fe, N-codoped carbon black by using 2-mercaptoethanol as an adhesive sulfur precursor. By the doping of trace S atoms (similar to 0.25 at%) into Fe, N-codoped carbon frameworks, the ORR performance has been obviously improved simply without any re-treatment process, such as acid-etching or nitrogen supplement. The mechanism of this process has been systematically investigated by changing the amount of initial sulfur precursor. A moderate amount of trace sulfur can effectively enhance the ORR performance of Fe, N-codoped carbon black due to suitable interactions among Fe, N, S and C elements. Both the content and the state of Fe and N species on the surface of carbon black can be changed and controlled by trace sulfur. The as-synthesized 1.0 S-Fe/N/C catalyst exhibits a good ORR activity (E-1/(2) = 0.749 V, J(k) = 54.56 mA cm(-2)) and a total 4-electron selectivity. 1.0 S-Fe/N/C also shows better catalytic stability and methanol tolerance than 20 wt% Pt/C. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.