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An innovative synthetic route that involves the thermal treatment of selected Ru co−ordination complexes was used to prepare RuO₂-based materials with catalytic activity for oxygen reduction (ORR) and oxygen evolution (OER) reactions. Extensive characterization confirmed the presence of Ru metal and RuP₃O₉ in the materials, with an improved electrocatalytic performance obtained from calcinated [(RuCl₂(PPh₃)₃]. A mechanistic approach for the obtention of such singular blends and for the synergetic contribution of these three species to electrocatalysis is suggested. Catalysts added to carbon−based electrodes were also tested in all−solid and flooded alkaline Zn/air batteries. The former displayed a specific discharge capacity of 10.5 A h g⁻¹ at 250 mA g⁻¹ and a power density of 4.4 kW kg⁻¹ cm⁻². Besides, more than 800 discharge/charge cycles were reached in the flooded alkaline Zn/air battery