Background and Objectives: Exposure to traffic is an established risk factor for the triggering of myocardial infarction (MI). Particulate matter, mainly emitted by diesel vehicles, appears to be the most important stressor. However, the possible influence of benzene from gasoline-fueled cars has not been explored so far. Methods and Results: We conducted a case-crossover study from 2,134 MI cases recorded by the local Coronary Heart Disease Registry (2000–2007) in the Strasbourg Metropolitan Area (France). Available individual data were age, gender, previous history of ischemic heart disease and address of residence at the time of the event. Nitrogen dioxide, particles of median aerodynamic diameter <10 µm (PM10), ozone, carbon monoxide and benzene air concentrations were modeled on an hourly basis at the census block level over the study period using the deterministic ADMS-Urban air dispersion model. Model input data were emissions inventories, background pollution measurements, and meteorological data. We have found a positive, statistically significant association between concentrations of benzene and the onset of MI: per cent increase in risk for a 1 µg/m3 increase in benzene concentration in the previous 0, 0–1 and 1 day was 10.4 (95% confidence interval 3–18.2), 10.7 (2.7–19.2) and 7.2 (0.3–14.5), respectively. The associations between the other pollutants and outcome were much lower and in accordance with the literature. Conclusion: We have observed that benzene in ambient air is strongly associated with the triggering of MI. This novel finding needs confirmation. If so, this would mean that not only diesel vehicles, the main particulate matter emitters, but also gasoline-fueled cars –main benzene emitters–, should be taken into account for public health action.