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The hydrolysis of CH2OO is not only a dominant sink for the CH2OO intermediate in the atmosphere but also a key process in the formation of aerosols. Herein, the reaction mechanism and kinetics for the hydrolysis of CH2OO catalyzed by the precursors of atmospheric aerosols, including H2SO4, H2SO4···H2O, and (H2SO4)2, have been studied theoretically at the CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2df,2pd) level. The calculated results show that the three catalysts decrease the energy barrier by over 10.3 kcal·mol–1; at the same time, the product formation of HOCH2OOH is more strongly bonded to the three catalysts than to the reactants CH2OO and H2O, revealing that small clusters of sulfuric acid promote the hydrolysis of CH2OO both kinetically and thermodynamically. Kinetic simulations show that the H2SO4-assisted reaction is more favorable than the H2SO4···H2O- (the pseudo-first-order rate constant being 27.9–11.5 times larger) and (H2SO4)2- (between 2.8 × 104and 3.4 × 105times larger) catalyzed reactions. Additionally, due to relatively lower concentration of H2SO4, the hydrolysis of CH2OO with H2SO4cannot compete with the CH2OO + H2O or (H2O)2reaction within the temperature range of 280–320 K, since its pseudo-first-order rate ratio is smaller by 4–7 or 6–8 orders of magnitude, respectively. However, the present results provide a good example of how small clusters of sulfuric acid catalyze the hydrolysis of an important atmospheric species.