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Abstract Catalytic water oxidation is an important process for the development of clean energy solutions and energy storage. Despite the significant number of reports on active catalysts, systematic control of the catalytic activity remains elusive. In this study, descriptors are explored that can be correlated with catalytic activity. [Ru(tpy)(pic)₂(H₂O)](NO₃)₂and [Ru(EtO‐tpy)(pic)₂(H₂O)](NO₃)₂(where tpy=2,2′ : 6′,2“‐terpyridine, EtO‐tpy=4′‐(ethoxy)‐2,2′:6′,2”‐terpyridine, pic=4‐picoline) are synthesized and characterized by NMR, UV/Vis, EPR, resonance Raman, and X‐ray absorption spectroscopy, and electrochemical analysis. Addition of the ethoxy group increases the catalytic activity in chemically driven and photocatalytic water oxidation. Thus, the effect of the electron‐donating group known for the [Ru(tpy)(bpy)(H₂O)]²⁺family is transferable to architectures with a tpy ligandtransto the Ru‐oxo unit. Under catalytic conditions, [Ru(EtO‐tpy)(pic)₂(H₂O)](NO₃)₂displays new spectroscopic signals tentatively assigned to a peroxo intermediate. Reaction pathways were analyzed by using DFT calculations. [Ru(EtO‐tpy)(pic)₂(H₂O)](NO₃)₂is found to be one of the most active catalysts functioning by a water nucleophilic attack mechanism.