Various advanced catalysts of sulfur doped Fe-N-C materials have been recently designed for oxygen reduction reaction (ORR), however, the enhanced activity is still controversial and usually attributed to differences in surface area, improved conductivity, or to uncertain synergistic effects. Here, a sulfur-doped Fe-N-C catalyst (denoted as Fe/SNC) derived via a template sacrificing method is presented. The incorporated S gives a thiophene-like structure (C-S-C), reduces the electron localization around the Fe center, improves the interaction with oxygenated species, and therefore facilitates the complete 4e- ORR in acid solution. This synergistic effect makes the Fe/SNC catalyst exhibits much better ORR activity than sulfur free catalyst (Fe/NC) in 0.5 M H2SO4.