This study is focused on the relative humidity (RH) dependence of water-soluble secondary organic aerosol (SOA) aging by photolysis. Particles containing a-pinene SOA and ammonium sulfate, generated by atomization, were exposed to UV radiation in an environmental chamber at three RH conditions (5, 45, and 85%), and changes in chemical composition and mass were monitored using an aerosol mass spectrometer (AMS). Under all RH conditions, photolysis leads to substantial loss of SOA mass, where the rate of mass loss decreased with decreasing RH. For all RH conditions, the less oxidized components of SOA (e.g., carbonyls) exhibited the fastest photodegradation rates, which resulted in a more oxidized SOA after photolytic aging. The photolytic reactivity of SOA material exhibited a dependence on RH likely due to moisture-induced changes in SOA morphology or phase. The results suggest that the atmospheric lifetime of SOA with respect to photolysis is dependent on its RH cycle, and that photolysis may be an important sink for some SOA components occurring on an initial time scale of a few hours under ambient condition