The development of international and national directives for air quality has seen application of the diffusive sampling technology to air quality assessment, expanding its field of application from its workplace origins to encompass ambient air quality, indoor air and, most recently, total exposure assessment. This study has applied the diffusive technique to assessment of environmental exposure to priority aromatic compounds found in urban environments, using commercially designed and compliant thermally desorbable diffusive sampling tubes. Pollutant concentrations were measured and compared at locations chosen to represent the outdoor environment of a suburban home, as affected by different modes of road transportation and traffic density. The relative contribution of indoor, outdoor, commuting and work activities to total exposure was also assessed. A detailed evaluation of uptake rate of the measured compounds to the sorbent was performed. These determinations were made at concentrations typically found in urban air for exposure times of several hours through to 4-weeks. A strong correlation of uptake rate with time was observed, the data following a power law dependence. Effective uptake rates for benzene, toluene, ethylbenzene, m- plus p-xylene and o-xylene on Tenax®GR sorbent were determined for use in the measurement of environmental concentrations, and applicable to short duration through to longer-term time-averaged air quality assessments. This paper presents a discussion of the methodology developed and of the results obtained.