Chile is a fast-growing country with important industrial activities near urban areas. In this study, the mass and elemental concentrations of PM10 and PM2.5 were measured in five major Chilean urban areas. Samples of particles with diameter less than 10 μm (PM10) and 2.5 μm (PM2.5) were collected in 1998 in Iquique (northern Chile), Valparaíso, Viña del Mar, Rancagua (central Chile), and Temuco (southern Chile). Both PM10 and PM2.5 annual mean concentrations (PM10: 56.9-77.6 μg/m3; PM2.5: 22.4-42.6 μg/m3) were significantly higher than the corresponding European Union (EU) and U.S. Environmental Protection Agency (EPA) air quality standards. Moreover, the 24-hr PM10 and PM2.5 U.S. standards were exceeded infrequently for some of the cities (Rancagua and Valparaíso). Elements ranging from Mg to Pb were detected in the aerosol samples using X-ray fluorescence (XRF). For each of the five cities, factor analysis (FA) was applied to identify and quantify the sources of PM10 and PM2.5. The agreement between calculated and measured mass and elemental concentrations was excellent in most of the cities. Both natural and anthropogenic sources were resolved for all five cities. Soil and sea were the most important contributors to coarse particles (PM10-PM2.5), whereas their contributions to PM2.5 were negligible. Emissions from Cu smelters and oil refineries (and/or diesel combustion) were identified as important sources of PM2.5, particularly in the industrial cities of Rancagua, Valparaíso, and Viña del Mar. Finally, motor vehicles and wood burning were significant sources of both PM2.5 and PM10 in most of the cities (wood burning was not identified in Iquique).