A family of Ru complexes based on the pentadentate t5a3- ligand ((2,5-bis(6-carboxylatopyridin-2- yl)pyrrol-1-ide) and pyridine (py) that include, {RuII(Ht5a--N2O)(py)3}, 1HII(-N2O), {RuIII(t5a-- N3O1.5)(py)2}, 2III(-N3O1.5) and {RuIV(t5a--N3O2)(py)2}+, {2IV(-N3O2)}+ has been prepared and thoroughly characterized. Complexes 1HII(-N2O), 2III(-N3O1.5) and {2IV(-N3O2)}+ have been investigated in solution by spectroscopic methods (NMR, UV-vis) and in the solid state by single- crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2III(-N3O1.5) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a3- ligand. In neutral to basic conditions complex {2IV(-N3O2)}+ undergoes aquation generating {RuIV(OH)(t5a--N2O)(py)2}, 2IV(OH)(-N2O). Further oxidation of the complex forms {RuV(O)(t5a--N2O)(py)2}, 2V(O)(-N2O) that is a very efficient water oxidation catalyst, reaching TOFMAX of 9400 s-1 at pH = 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2V(O)(-N2O) is due to not only the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the non- coordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.