Ambient air pollution is associated with numerous adverse health impacts. Previous assessments of global attributable disease burden have been limited to urban areas or by coarse spatial resolution of concentration estimates. Recent developments in remote sensing, global chemical-transport models, and improvements in coverage of surface measurements facilitate virtually complete spatially resolved global air pollutant concentration estimates. We combined these data to generate global estimates of long- term average ambient concentrations of fine particles (PM_2.5) and ozone at 0.1° × 0.1° spatial resolution for 1990 and 2005. In 2005, 89% of the world’s population lived in areas where the World Health Organization Air Quality Guideline of 10 μg/m³ PM_2.5 (annual average) was exceeded. Globally, 32% of the population lived in areas exceeding the WHO Level 1 Interim Target of 35 μg/m³; driven by high proportions in East (76%) and South (26%) Asia. The highest seasonal ozone levels were found in North and Latin America, Europe, South and East Asia, and parts of Africa. Between 1990 and 2005 a 6% increase in global population-weighted PM_2.5 and a 1% decrease in global population- weighted ozone concentrations was apparent, highlighted by increased concentrations in East, South and Southeast Asia and decreases in North America and Europe. Combined with spatially resolved population distributions, these estimates expand the evaluation of the global health burden associated with outdoor air pollution.