Benzene is classified as a Group I carcinogen by the International Agency for Research on Cancer (IARC). The risk assessment for benzene can be performed by monitoring environmental and occupational air, as well as biological monitoring through biomarkers. The present work developed and validated methods for benzene analysis by GC/MS using SPME as the sampling technique for ambient air and breath. The results of the analysis of air in parks and avenues demonstrated a significant difference, with average values of 4.05 and 18.26 microg m(-3), respectively, for benzene. Sampling of air in the occupational environment furnished an average of 3.41 and 39.81 microg m(-3). Moreover, the correlations between ambient air and expired air showed a significant tendency to linearity (R (2) = 0.850 and R (2) = 0.879). The results obtained for two groups of employees (31.91 and 72.62 microg m(-3)) presented the same trend as that from the analysis of environmental air.