The chemical constituents of fine particulate matter (PM2.5) vary by source and capacity to participate in redox reactions in the body, which produce cytotoxic reactive oxygen species (ROS). Knowledge of the sources and components of PM2.5 may provide insight into the adverse health effects associated with the inhalation of PM2.5 mass. We collected 48 h household and personal PM2.5 exposure measurements in the summer months among 50 women/household pairs in a rural area of southwestern China where daily household biomass burning is common. PM2.5 mass was analyzed for ions, trace metals, black carbon, and water-soluble organic matter, as well as ROS-generating capability (oxidative potential) by one cellular and one acellular assay. Crustal enrichment factors and a principal component analysis identified the major sources of PM2.5 as dust, biomass burning, and secondary sulfate. Elements associated with the secondary sulfate source (As, Mo, Zn) had the strongest correlation with increased cellular oxidative potential (Spearman r: 0.74, 0.68, and 0.64). Chemical markers of biomass burning (water-soluble potassium and water-soluble organic matter) had negligible oxidative potential, suggesting that these assays may not be useful as health-relevant exposure metrics in populations that are exposed to high levels of smoke from household biomass burning.