<p><strong>Abstract.</strong> Urbanisation is a strongly emerging issue in Southern West African (SWA) region. There is a general lack of understanding about the personal exposure to fine particulate matter (PM<sub>2.5</sub>), its chemical components and health risks related to the various anthropogenic sources in this region. In the current study, personal exposure to PM<sub>2.5</sub> (PE PM<sub>2.5</sub>) sampling was for the first time carried out in dry season (January) and wet season (July) of 2016 to characterize PE PM<sub>2.5</sub> from Domestic Fires (DF) for women and Waste Burning (WB) for students in Abidjan, C&#244;te d'Ivoire and Motorcycle Traffic (MT) for drivers in Cotonou, Benin.</p> <p>The average PE PM<sub>2.5</sub> mass concentrations were 331.7&#8201;&#177;&#8201;190.7, 356.9&#8201;&#177;&#8201;71.9 and 242.8&#8201;&#177;&#8201;67.6&#8201;&#956;g&#8201;m<sup>&#8722;3</sup> at DF, WB and MT for women, students and drivers, which were 2.4, 10.3 and 6.4 times of the ambient PM<sub>2.5</sub> concentrations, respectively. Mean concentrations of PE PM<sub>2.5</sub> at DF (358.8&#8201;&#177;&#8201;100.5&#8201;&#956;g&#8201;m<sup>&#8722;3</sup>), WB (494.3&#8201;&#177;&#8201;15.8&#8201;&#956;g&#8201;m<sup>&#8722;3</sup>) and MT (335.1&#8201;&#177;&#8201;72.1&#8201;&#956;g&#8201;m<sup>&#8722;3</sup>) were much elevated in dry season, 15&#8201;% higher than that at DF and 55&#8201;% higher at both WB and MT. The changes in PE PM<sub>2.5</sub> can be attributed to the source emissions, meteorological factors and personal activities. The results also show that geological material (35.8&#8201;%, 46.0&#8201;% and 42.4&#8201;%) and organic matter (34.1&#8201;%, 23.3&#8201;% and 24.9&#8201;%) were always the major components in PE PM<sub>2.5</sub> at DF, WB and MT sites. It is worth noting that the contribution to PE PM<sub>2.5</sub> from heavy metals was higher at WB (1.0&#8201;%) than at DF (0.7&#8201;%) and MT (0.4&#8201;%), which was influenced by the waste burning emission strongly, leading to the highest heavy metal non-cancer risks for students (5.1 and 4.8 times of women and drivers' non-cancer risks).</p> <p>In organic species of PE PM<sub>2.5</sub>, some fingerprints can be used to quantify the exposure concentrations and trace the source contributions from local typical anthropogenic sources to different samples. Women exposure concentration to polycyclic aromatic hydrocarbons (PAHs) in PM<sub>2.5</sub> at DF (77.4&#8201;&#177;&#8201;47.9&#8201;ng&#8201;m<sup>&#8722;3</sup>) was 1.6 times that for students at WB (49.9&#8201;&#177;&#8201;30.7&#8201;ng&#8201;m<sup>&#8722;3</sup>) and 2.1 times for drivers at MT (37.0&#8201;&#177;&#8201;7.4&#8201;ng&#8201;m<sup>&#8722;3</sup>), which is related to the solid fuels burning and grilling meat activities, resulting in 5 times higher of cancer risk safety threshold (1&#8201;&#215;&#8201;10<sup>&#8722;6</sup>) to women. Phthalate esters (PAEs), commonly used as plasticizers in many products, were observed to be extremely high in student exposure PM<sub>2.5</sub> samples (1380.4&#8201;&#177;&#8201;335.2&#8201;ng&#8201;m<sup>&#8722;3</sup>) at WB site, owing to the waste burning emission obviously. Drivers exposure to fossil fuel emission (especially traffic) markers-hopanes in PE PM<sub>2.5</sub> at MT (50.9&#8201;&#177;&#8201;7.9&#8201;ng&#8201;m<sup>&#8722;3</sup>) was 2.0&#8211;2.3 times higher than women at DF (17.1&#8201;&#177;&#8201;6.4&#8201;g&#8201;m<sup>&#8722;3</sup>) and students at WB (15.6&#8201;&#177;&#8201;6.1&#8201;ng&#8201;m<sup>&#8722;3</sup>), correlating with the elevated exposure to traffic emissions for drivers.</p> <p>Overall, the study shows that wood combustion, waste burning, fugitive dust and motor vehicle emissions dominated PE PM<sub>2.5</sub> mass and contributed to its toxicities mainly. Heavy metals and organic chemicals in PE PM<sub>2.5</sub> in SWA brought about Pb and Mn non-cancer health risks for students at WB site and serious PAHs cancer risks for women at DF site via inhalation pathway. This study provides basic data and initial perspective of PM<sub>2.5</sub> personal exposure and health risk assessment in underdeveloped area to encourage the government to improve the air quality and living standard of residents in this region.</p>