Secondary organic aerosol (SOA) comprises most of the submicron atmospheric particle mass, and often becomes internally mixed with other particles. When SOA mixes with transition metal (e.g., iron) containing particles, metal-organic complexes can form, enabling photochemical reactions that change aerosol physicochemical properties. We studied the photochemistry of α-pinene SOA formed on iron-containing ammonium sulfate seed particles at varying relative humidities (RH). Chemical composition and photochemical reduction of particles were analyzed by X-ray spectromicroscopy and infrared spectroscopy. SOA formed at low vs. high RH had different chemical functionality, including abundant carboxylic acids and alcohols. Following photolysis, carboxylic acids and unsubstituted alkanes decreased, and alcohols increased, consistent with decarboxylation reactions. Iron in SOA formed at high RH was readily photochemically reduced, but iron in SOA formed at low RH was not. Overall, RH conditions at SOA formation affect not only chemical composition but also iron-complex formation and hence photochemical processing of aerosols.