The recently described solid solution (Co,Ni,Mn)3Sb4O6F6has proved stable and efficient as a catalyst for electrocatalytic water oxidation. The end component Co3Sb4O6F6was found to be most efficient, maintaining a current density ofj= 10 mA cm−2at an overpotential of 443 mV with good capability. At this current density, O2and H2were produced in the ratio 1 : 2 without loss of faradaic current against a Pt-cathode. A morphological change in the crystallite surface was observed after 0.5 h, however, even after 64.5 h, the overall shape and size of the small crystallites were unaffected and the electrolyte contained only 0.02 at% Co. It was also possible to conclude fromin situEXAFS measurements that the coordination around Co did not change. The oxofluorides express both hydrophilic and hydrophobic surface sites, incorporate a flexible metalloid element and offer the possibility of a mechanism that differs from other inorganic catalytic pathways previously described.