Exposure to particulate matter (PM) and its chemical constituents in residential microenvironments has become a major health concern worldwide. The oxidative potential (OP) has been proposed as a metric for estimating the PM capacity to induce oxidative stress and, consequently, health effects. In the present study, PM10 was daily monitored simultaneously in the bedroom, living room and kitchen of three dwellings for one week in a small town of Portugal, to perform a detailed characterisation of its organic and inorganic constituents and the determination of the OP. Bedrooms (B) were found to be a hotspot of PM10 concentrations (B1 = 22.7 μg m−3; B2 = 19.5 μg m−3; B3 = 68.1 μg m−3). PM10-bound elements varied significantly between microenvironments in all dwellings. Lower molecular weight polycyclic aromatic hydrocarbons (PAHs) were found to be between 14 and 72 times higher than high molecular weight PAHs in bedrooms. The mean volume-normalised OP determined by the dithiothreitol and ascorbic acid assays varied within the 0.01–0.38 nmol min−1 m−3 and 0.03–0.53 nmol min−1 m−3 ranges, respectively. Quinones, oxy-aromatic, aromatic and alkyl-aromatic compounds stood out in bedrooms. Strong and significantly positive relationship between OP and black carbon, Cu and Br were observed, indicating common redox active species mainly associated with traffic emissions. Sr, Fe, Zn and Zr presented higher concentrations in dwelling 3, exhibiting excellent positive correlation with OP, indicating that the Sahara dust intrusion recorded in that house may have contributed to the formation of more redox active species thought to drive antioxidant depletion responses.