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Since the potential inversion behavior of a Ru–aqua complex during the sequential, proton‐coupled, two‐electron oxidations, RuII─OH2 → RuIVO via RuIII─OH, has been experimentally confirmed, the calculation method for predicting this phenomenon becomes necessary for the rational design of such complexes. Here, we devise cost‐effective calculation protocols that properly describe sequential, proton‐coupled, two‐electron oxidation reactions. The suggested protocols are: (1) by use of an mPW1LYP hybrid functional coupled with a LANL2DZ basis set with an effective core potential (ECP) for transition metal, and a 6‐31g(d) basis set for the rest of atoms; and (2) by use of a PBE1PBE hybrid functional with a def2SVP basis set for all atoms, and an Stuttgart RSC 1997 ECP for transition metal. With these protocols, we demonstrated that a Meyer–Lever plot of six representative Ru–aqua complexes, in which atoms of the ligands are second‐row elements, can be satisfactorily reproduced. [ABSTRACT FROM AUTHOR]