Photoinduced volatile organic compounds (VOCs) release from fatty alcohols at the air-water interface, has attracted considerable attention. This paper comprehensively explores the release of odorous VOCs from aqueous micropollutants under photoirradiation, especially in terms of the important role of the reactive oxygen species (ROS) in increased risk by cross-media transformation. The formation and distribution of photoinduced VOCs produced by aqueous benzyl alcohol (BzOH), a common ingredient in personal care products, were monitored in situ by online gas chromatography equipped with mass spectrometry and flame ionization detector (GC–MS/FID). The photoreaction of BzOH followed first-order kinetics with a rate constant of 0.0158/min under air. After 180 min of ultraviolet irradiation, the accumulated output of the gas-phase products benzene and benzaldehyde (BA) reached 3.8 μmol and 2.6 μmol respectively, being approximately 10 times that under nitrogen. According to electron paramagnetic resonance measurements, singlet oxygen mainly promoted the oxidation of BzOH to BA, which was an important intermediate producing benzene via photocleavage. Odorous alicyclic hydrocarbons were also generated through photorearrangement under nitrogen. On the other hand, the Henry's law constants of the main products were much lower than those of BzOH, indicating that the photoproducts would volatilize from the aqueous phase into the gas phase. The odor threshold of gas-phase products decreased to varying degrees after photoirradiation. Especially for BA, one of the main products, its odor threshold decreased 130 times compared with BzOH. This study shows that the risk of cross-media pollution could significantly increase due to the transformation of aqueous pollutants into odorous VOCs under photoirradiation and provides new insight into its risk prevention.