Accurate assessment of human exposures is an important part of environmental health effects research. However, most air pollution epidemiology studies rely upon imperfect surrogates of personal exposures, such as information based on available central-site outdoor concentration monitoring or modeling data. In this paper, we examine the limitations of using outdoor concentration predictions instead of modeled personal exposures for over 30 gaseous and particulate hazardous air pollutants (HAPs) in the US. The analysis uses the results from an air quality dispersion model (the ASPEN or Assessment System for Population Exposure Nationwide model) and an inhalation exposure model (the HAPEM or Hazardous Air Pollutant Exposure Model, Version 5), applied by the US. Environmental protection Agency during the 1999 National Air Toxic Assessment (NATA) in the US. Our results show that the total predicted chronic exposure concentrations of outdoor HAPs from all sources are lower than the modeled ambient concentrations by about 20% on average for most gaseous HAPs and by about 60% on average for most particulate HAPs (mainly, due to the exclusion of indoor sources from our modeling analysis and lower infiltration of particles indoors). On the other hand, the HAPEM/ASPEN concentration ratio averages for onroad mobile source exposures were found to be greater than 1 (around 1.20) for most mobile-source related HAPs (e.g. 1, 3-butadiene, acetaldehyde, benzene, formaldehyde) reflecting the importance of near-roadway and commuting environments on personal exposures to HAPs. The distribution of the ratios of personal to ambient concentrations was found to be skewed for a number of the VOCs and reactive HAPs associated with major source emissions, indicating the importance of personal mobility factors. We conclude that the increase in personal exposures from the corresponding predicted ambient levels tends to occur near locations where there are either major emission sources of HAPs or when individuals are exposed to either on- or nonroad sources of HAPs during their daily activities. These findings underscore the importance of applying exposure-modeling methods, which incorporate information on time-activity, commuting, and exposure factors data, for the purposes of assigning exposures in air pollution health studies.