Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of toluene/CH 3ONO/NO x mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer (FTIR). Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups (C O), hydroxyl groups ( OH), carboxylic acid ( COOH), C C bonding, N O bonding and C H bonding (C H), was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer (ATOFMS). It was found that there are some differences between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while ketones, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.