SO2 influences secondary organic aerosol (SOA) and organosulfates (OSs) formation but mechanisms remain elusive. This study focuses on this topic by investigating biogenic γ-terpinene ozonolysis under various SO2 and relative humidity (RH) conditions. With a constant SO2 concentration (∼110 ppb), the increase in RH transformed SO2 sinks from stabilized Criegee intermediates (sCIs) to peroxides in aerosol particles. The associated changes in particle acidity and liquid water content may collectively first lead to decreased and then increased SOA yield with increasing RH, with the turning point appearing at ∼30% RH. The abundance of most OSs formed under 45% RH was more than 5 times higher than that of OSs formed under 10% RH, possibly due to interactions of dissolved SO2 with hydroperoxides (ROOH) in SOA. ROOHs formed from the autoxidation processes of alkylperoxy radicals were proposed to be precursors for highly oxidized OSs (HOOSs) that decreased SOA volatility and showed a certain abundance in ambient aerosols. This study highlights that high RH potentially enhances the contribution of SO2 to OSs formation, and particularly, HOOSs formation during monoterpene ozonolysis in the atmosphere.