Abstract Transition metal sulfides have been demonstrated to be more active electrocatalysts than the corresponding (hydr)oxides for oxygen evolution reaction (OER). The nature of active sites, however, remains unclear. Here, we study whether S could promote the OER activity of FeCoOOH and try to identify the catalytically active centers. Density functional theory suggests that two coordinating S could work synergistically with one adjacent Fe to optimize the electronic states of Co, resulting in decreased binding energy of OH∗ (ΔE ) while little changed ΔE , and thus significantly loweri...