While ambient air pollution levels in excess of prescribed health standards are generally unacceptable, the exceedance is even more serious in areas where people reside. Vulnerability caused by poverty, disease, lack of education, and poor living conditions exacerbates the problem. Air quality management plans identify prioritized strategies for improved air quality independent of consideration of vulnerability. A population exposure and vulnerability risk prioritization framework comprising five themes (air pollution sources and levels; air pollution potential; community awareness, observations, perceptions, and actions; and vulnerability factors) was proposed and applied to the eThekwini Municipality (Durban, South Africa). Data were scored according to predetermined risk threshold values to ascertain at-risk communities. While those urban wards located in a known air pollution hotspot had the highest air pollution levels, a periurban ward with moderate exposure levels was most vulnerable. This framework will prove invaluable for the development of focused interventions to reduce vulnerability and air pollution–associated adverse health impacts.