Exposure to airborne particulates is estimated as the largest cause of premature human mortality worldwide and is of particular concern in sub-Saharan Africa where emissions are high and data are lacking. Particulate matter (PM) contains several toxic organic species including polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs (NPAHs). This study provides the first characterization and source identification for PM10- and PM2.5-bound PAHs and NPAHs in sub-Saharan Africa during a three-month period that spanned dry and wet seasons at three locations in Rwanda. The 24-h mean PM2.5 and PM10 concentrations were significantly higher in the dry than the wet season. PAH and NPAH concentrations at the urban roadside site were significantly higher than the urban background and rural site. Source identification using diagnostic ratio analysis and principal component analysis (PCA) revealed diesel and gasoline-powered vehicles at the urban location and wood burning at the rural location as the major sources of PAHs and NPAHs. Our analysis demonstrates that PM concentrations and lifetime cancer risks resulting from inhalation exposure to PM-bound PAHs and NPAHs exceed World Health Organization safe limits. This study provides clear evidence that an immediate development of emission control measures is required.