To reveal the role of ferrate self-decomposition and the fates of intermediate iron species [Fe(V)/Fe(IV) species] during ferrate oxidation, the reaction between ferrate and methyl phenyl sulfoxide (PMSO) at pH 7.0 was investigated as a model system in this study. Interestingly, the apparent second-order rate constants (k_app) between ferrate and PMSO was found to increase with ferrate dosage in the condition of excess ferrate in borate buffer. This ferrate dosage effect was diminished greatly in the condition of excess PMSO where ferrate self-decomposition was lessened largely, or counterbalanced by adding a strong complexing ligand (e.g. pyrophosphate) to sequester Fe(V) oxidation, demonstrating that the Fe(V) species derived from ferrate self-decomposition plays an important role in PMSO oxidation. A mechanistic kinetics model involving the ferrate self-decomposition and PMSO oxidation by Fe(VI), Fe(V) and Fe(IV) species was then developed and validated. The modeling results show that up to 99% of the PMSO oxidation was contributed by the ferrate self-decomposition resultant Fe(V) species in borate buffer, revealing that ferrate self-decomposition is also a self-activation process. The direct Fe(VI) oxidation of PMSO was impervious to presence of phosphate or Fe(III), while the Fe(V) oxidation pathway was strongly inhibited by phosphate complexation or enhanced with Fe(III). Similar ferrate dosage effect and its counterbalance by pyrophosphate as well as the Fe(III) enhancement were also observed in ferrate oxidation of micropollutants like carbamazepine, diclofenac and sulfamethoxazole, implying the general role of Fe(V) and promising Fe(III) enhancement during ferrate oxidation of micropollutants.