Toxic air pollutants in street canyons are important issues concerning public health especially in some large Asian cities like Guangzhou. In 1998 <18% of Guangzhou citizens used public transportation modes, with a majority commuting on foot (42%) or by bicycle (22%). Of the pedestrians, 57% were either senior citizens or students. In the present study, we measured toxic air pollutants while walking along urban streets in Guangzhou to evaluate pedestrian exposure. Volatile organic compounds (VOCs) were collected with sorbent tubes, and PM 10 and CO were measured simultaneously with portable analyzers. Our results showed that pedestrian exposure to PM 10 (with an average of 303 μg m -3 for all samples) and some toxic VOCs (for example, benzene) was relatively high. Monocyclic aromatic hydrocarbons were found to be the most abundant VOCs, and 71% of the samples had benzene levels higher than 30 μg m -3. Benzene, PM 10 and CO in walk-only streets were significantly lower (p<0.05) than in traffic streets, and the differences in exposure levels between new urban streets and old urban streets were highly significant (p<0.01). Pedestrian exposure to toxic VOCs and PM 10 was higher than those reported in other public transportation modes (bus and subway). The good correlations between BTEX, PM 10 and CO in the streets indicated that automotive emission might be their major source. Our study also showed that the risk to pedestrians due to air pollution was misinterpreted by the reported air quality index based on measurement of SO 2, NO x and PM 10 in the government monitoring stations. An urban roadside monitoring station might be needed by air quality monitoring networks in large Asian cities like Guangzhou, in order to survey exposure to air toxics in urban roadside microenvironments. © 2004 Elsevier Ltd. All rights reserved.