Using Multi-angle Imaging SpectroRadiometer (MISR) and sub-orbital measurements from the 2006 INTEX-B/MILAGRO field campaign, in this study we explore MISR’s ability to map different aerosol air mass types over the Mexico City metropolitan area. The aerosol air mass distinctions are based on shape, size and single scattering albedo retrievals from the MISR Research Aerosol Retrieval algorithm. In this region, the research algorithm identifies dust-dominated aerosol mixtures based on non-spherical particle shape, whereas spherical biomass burning and urban pollution particles are distinguished by particle size. Two distinct aerosol air mass types based on retrieved particle microphysical properties, and four spatially distributed aerosol air masses, are identified in the MISR data on 6 March 2006. The aerosol air mass type identification results are supported by coincident, airborne high-spectral-resolution lidar (HSRL) measurements. Aerosol optical depth (AOD) gradients are also consistent between the MISR and sub-orbital measurements, but particles having single-scattering albedo of ≈ 0.7 at 558 nm must be included in the retrieval algorithm to produce good absolute AOD comparisons over pollutiondominated aerosol air masses. The MISR standard V22 AOD product, at 17.6 km resolution, captures the observed AOD gradients qualitatively, but retrievals at this coarse spatial scale and with limited spherical absorbing particle options underestimate AOD and do not retrieve particle properties adequately over this complex urban region. However, we demonstrate how AOD and aerosol type mapping can be accomplished with MISR data over complex urban regions, provided the retrieval is performed at sufficiently high spatial resolution, and with a rich enough set of aerosol components and mixtures.