Fine particulate matter (PM2.5) was monitored at five rural background locations in France from 2012 to 2021. Annual PM2.5 ranged from 5 to 15 μg m–3, all sites repeatedly exceeding the 2021 annual World Health Organization guideline. Chemical speciation including organic and elemental carbon (OC, EC), secondary inorganic aerosols (SIA: NO3–, SO42–, NH4+) and other major water-soluble ions (Cl–, Na+, Mg2+, Ca2+, K+) were monitored on 24-h filters covering 14% of the year. A source apportionment of OM was undertaken based on fine potassium and using representative ratios for domestic biomass burning (BB) and fossil fuel (FF) emissions. The latter dominated the EC fraction (55–60%) while BB was the main primary source of OM (27–54%). The average mass balance of PM2.5 at the French rural background atmospheric sites was: secondary organic aerosol (18–35%), BB (17–27%), non-sea-salt sulphate (12–17%), nitrate (6–22%), ammonium (7–11%), FF (4–6%), mineral dust (3–9%) and sea salt (1–2%). Secondary aerosols were the main component of PM2.5 through all seasons, with SIA dominating in spring episodes. The contribution of OM to PM2.5 was larger at the southern sites whereas the contribution of SIA was larger at the northern sites. The mean OC/EC ratio and the good correlations between OC, EC, and fine potassium suggested that BB was the main primary source contributing to carbonaceous aerosols, 27–54% to total OM depending on the site; and also, to PM2.5 (17–27%). Stronger regulations of OM sources including BB, nitrate from combustion, and ammonium from agricultural sources are needed to reduce PM2.5 at rural background sites on an annual and episodic basis, respectively.