The U.S. EPA periodically evaluates ambient concentrations, human exposures, and health risks for 180 hazardous air pollutants plus diesel particulate matter using modeled estimates from the National-Scale Air Toxics Assessment (NATA). NATA publishes estimates at the spatial resolution of U.S. Census tracts, which are subdivisions of a county. These local scale, model-predicted estimates from NATA are used extensively in community-based assessments; however, evaluation of NATA’s ambient concentrations and human exposure estimates against measurement data has been limited to date. This paper compares modeled annual average benzene results from the 2002 NATA with measured results from the 2004 to 2007 Detroit Exposure and Aerosol Research Study (DEARS) as a case study of the quality of NATA results. NATA model estimates support community-scale characterization and assessment. Benzene is particularly important as it was estimated by the 2002 NATA as the largest single air toxic pollutant in terms of cancer risk in the U.S. We found that the average ambient concentrations of benzene predicted by NATA were within 5 percent, on average, of the 24-h integrated average ambient concentrations measured in DEARS. The NATA human exposure estimates, which include only outdoor sources for benzene, were, on average, approximately half the measured breathing zone concentrations from DEARS. Our analyses support that the factors driving higher DEARS personal benzene concentrations relative to the NATA predicted exposure values are likely due, at least in part, to indoor sources. This work points to further community-scale modeling research to improve characterizations and assessments of human exposures.