In the atmosphere, carbonyl oxides known as Criegee intermediates are produced mainly by ozonolysis of volatile organic compounds containing CC double bonds, such as biogenic terpenoids. Criegee intermediates can react with OH-containing species to produce labile organic hydroperoxides (ROOHs) that are taken up into atmospheric condensed phases. Besides water, alcohols are an important reaction partner of Criegee intermediates and can convert them into α-alkoxyalkyl-hydroperoxides (α-AHs), R₁R₂C(–OOH)(–OR′). Here, we report a study on the aqueous-phase fates of α-AHs derived from ozonolysis of α-terpineol in the presence of methanol, ethanol, 1-propanol, and 2-propanol. The α-terpineol α-AHs and the decomposition products were detected as their chloride adducts by electrospray mass spectrometry as a function of reaction time. Our discovery that the rate of decomposition of α-AHs increased as the pH decreased from 5.9 to 3.8 implied that the decomposition mechanism was catalyzed by H⁺. The use of isotope solvent experiments revealed that a primary decomposition product of α-AHs in an acidic aqueous solution was a hemiacetal R₁R₂C(–OH)(–OR′) species that was further transformed into other products such as lactols. The proposed H⁺-catalyzed decomposition of α-AHs, which provides H₂O₂ and multifunctional species in ambient aerosol particles, may be faster than other degradation processes (e.g., photolysis by solar radiation).