This study presents the results of a paper of urban spatial structure and exceedances of the 8-h national ambient air quality standard for ozone in 45 large US metropolitan regions. Through the integration of a published index of sprawl with metropolitan level data on annual ozone exceedances, precursor emissions, and regional climate over a 13-year period, the association between the extent of urban decentralization and the average number of ozone exceedances per year, while controlling for precursor emissions and temperature, is measured. The results of this analysis support the hypothesis that large metropolitan regions ranking highly on a quantitative index of sprawl experience a greater number of ozone exceedances than more spatially compact metropolitan regions. Importantly, this relationship was found to hold when controlling for population size, average ozone season temperatures, and regional emissions of nitrogen oxides and volatile organic compounds, suggesting that urban spatial structure may have effects on ozone formation that are independent of its effects on precursor emissions from transportation, industry, and power generation facilities.