alpha-Keto acids are important, atmospherically relevant species, and their photochemistry has been considered in the formation and processing of aerosols. Despite their atmospheric relevance, the photochemistry of these species has primarily been studied under extremely low pH conditions. Using a variety of analytical techniques, we characterize the extent of hydration and deprotonation for solutions of two alpha-keto acids, pyruvic acid and 2-oxooctanoic acid, as a function of pH. We find that changes in the initial solution composition govern the accessibility of different photochemical pathways, resulting in slowed photolysis under high pH conditions and a shift in photoproducts that can be predicted mechanistically.