The generation of harmful by-products during photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a bottleneck problem for the application of PCO technology in indoor environrnent. Toluene is a typical VOC found in indoor air. In this work, the by-products at ppb level were studied during PCO decomposition of toluene in a plate-type reactor and identified using PTR-MS (proton transfer reaction-mass spectrometry)and CC-MS(gas chromatography-mass spectroscopy). The results indicated that benzaldehyde, methanol, acetaldehyde, acetone/propionaldehyde, formic acid/ethanol and acetic acid were the main by-products in the gas phase. By adjusting the concentration of water vapor, Some Compounds adsorbed on the TiO2 surface were ascertained, which resulted in the deactivation of TiO2. They were benzoic acid, benzene, acrylaldehyde, butyraldehyde and pentanal. Some of these by-products have not been reported in the literature. Possible photocatalytic oxidation Pathways of toluene were proposed. A health-related index (HRI) was introduced to assess the risk level to human health of these ppb-level by-products. It concludes that although some undesired by-products (even carcinogenic) are generated during PCO decomposition of toluene, it seems that these by-products do not have negative effects to human health because of their low concentrations. (C) 2009 Elsevier B.V. All rights reserved.