Abstract The kinetics and mechanism of the action of octanuclear ruthenium catalysts for the oxidation of water by Ce(IV) compounds in artificial photosynthesis are studied. The catalysts are obtained from K3[Ru2(μ-N)Cl8] · 2H2О complex via self-organization. It is established that [Ru-(μ-N)-Ru]4 octanuclear clusters form upon the tetramerization of the binuclear nitride complex and catalyze the eight-electron oxidation of water to two oxygen molecules. Only tetranuclear clusters that oxidize water in four-electron reaction to one oxygen molecule form at high temperatures (>60°С).