The ability of gold nanoparticles (AuNPs) to catalyze reactions involving radicals is poorly studied. However, AuNPs are used in applications where chemical reactions involving transient radicals occur. Herein, we investigate AuNPs’ catalytic effect on 2-propanol oxidation and acetanilide hydroxylation in aqueous solutions under ionizing radiation at room temperature. In both cases, the presence of AuNPs led to selective oxidation of organic radicals, significantly changing the products’ composition and ratio. Based on these observations, we stress how AuNPs’ catalytic activity can affect the correctness of reactive oxygen species concentration determination utilizing organic dyes. We also provide a discussion on the role of AuNPs’ catalytic activity in the radiosensitization effect actively studied for radiotherapy.