Often, in studies evaluating the health effects of hazardous air pollutants (HAPs), researchers rely on ambient air levels to estimate exposure. Two potential data sources are modeled estimates from the U.S. Environmental Protection Agency (EPA) Assessment System for Population Exposure Nationwide (ASPEN) and ambient air pollutant measurements from monitoring networks. The goal was to conduct comparisons of modeled and monitored estimates of HAP levels in the state of Texas using traditional approaches and a previously unexploited method, concordance correlation analysis, to better inform decisions regarding agreement. Census tract-level ASPEN estimates and monitoring data for all HAPs throughout Texas, available from the EPA Air Quality System, were obtained for 1990, 1996, and 1999. Monitoring sites were mapped to census tracts using U.S. Census data. Exclusions were applied to restrict the monitored data to measurements collected using a common sampling strategy with minimal missing values over time. Comparisons were made for 28 HAPs in 38 census tracts located primarily in urban areas throughout Texas. For each pollutant and by year of assessment, modeled and monitored air pollutant annual levels were compared using standard methods (i.e., ratios of model-to-monitor annual levels). Concordance correlation analysis was also used, which assesses linearity and agreement while providing a formal method of statistical inference. Forty-eight percent of the median model-to-monitor values fell between 0.5 and 2, whereas only 17% of concordance correlation coefficients were significant and greater than 0.5. On the basis of concordance correlation analysis, the findings indicate there is poorer agreement when compared with the previously applied ad hoc methods to assess comparability between modeled and monitored levels of ambient HAPs.