The kinetics of the oxidation of leuco methylene blue and leuco thionine by some p‐benzoquinones were investigated spectrophotometrically by means of the stopped‐flow technique. Leuco methylene blue and leuco thionine were produced by photoreductions of methylene blue and thionine with triethylamine in ethanol in the drive syringe of the stopped‐flow apparatus and their solutions were used as such in the measurement of the oxidation rates. The kinetic isotope effect on the oxidation rate was observed. The results can be explained by the general mechanism with stepwise electron–proton–‐electron transfers.