Annoyance produced by air pollution has been suggested as a useful proxy for determining ambient air pollution exposure. However, most of the studies, to date, have focused on nitrogen dioxide and sulphur dioxide, with no work done on volatile organic compounds (VOC). This study is aimed at examining the associations between odour annoyance and VOC in 'Chemical Valley', Sarnia, Ontario, Canada. Annoyance scores were extracted from a community health survey (N = 774), and exposures to VOC were estimated from respondents' six-digit alphanumeric postal codes using land use regression models. Univariate analyses were used to explore the relationships between odour annoyance and modelled pollutants, whilst multivariate ordinal logistic regression was utilized to examine the determinants of odour annoyance. The results indicate that odour annoyance is significantly associated with modelled benzene, toluene, ethylbenzene, o-xylene and (m + p) xylene (BTEX) pollutants. The findings also show that the determinants of odour annoyance in the context of VOC include gender, number of relatives in the community, perception of air pollution, community satisfaction, medical checkups, ability to cope with daily life demands and general symptoms. When compared, the analysis indicates that Sarnia residents respond to considerably lower BTEX concentrations than the allowable 'safe' levels in the province of Ontario. In general, the results exhibit a dose-response gradient with annoyance score increasing with rising modelled pollutant concentrations. The observed relationships suggest that odour annoyance might be a function of true exposure and may serve as a proxy for air quality and ambient air pollution monitoring. However, questionnaire-based odour annoyance scores need to be longitudinally validated across different geographical scales and pollutants if they are to be adopted at the national level.