A growing number of studies are using specific primary sugar species, such as sugar alcohols or primary saccharides, as marker compounds to characterize and apportion primary biogenic organic aerosols (PBOAs) in the atmosphere. To better understand their annual cycles, as well as their spatiotemporal abundance in terms of concentrations and sources, we conducted a large study focusing on three major atmospheric primary sugar compounds (i.e., arabitol, mannitol, and glucose) measured in various environmental conditions for about 5300 filter samples collected at 28 sites in France. Our results show significant atmospheric concentrations of polyols (defined here as the sum of arabitol and mannitol) and glucose at each sampling location, highlighting their ubiquity. Results also confirm that polyols and glucose are mainly associated with the coarse rather than the fine aerosol mode. At nearly all sites, atmospheric concentrations of polyols and glucose display a well-marked seasonal pattern, with maximum concentrations from late spring to early autumn, followed by an abrupt decrease in late autumn, and a minimum concentration during wintertime. Such seasonal patterns support biogenic emissions associated with higher biological metabolic activities (sporulation, growth, etc.) during warmer periods. Results from a previous comprehensive study using positive matrix factorization (PMF) based on an extended aerosol chemical composition dataset of up to 130 species for 16 of the same sample series have also been used in the present work. The polyols-to-PMPBOA ratio is 0.024±0.010 on average for all sites, with no clear distinction between traffic, urban, or rural typology. Overall, even if the exact origin of the PBOA source is still under investigation, it appears to be an important source of particulate matter (PM), especially during summertime. Results also show that PBOAs are significant sources of total organic matter (OM) in PM10 (13±4 % on a yearly average, and up to 40 % in some environments in summer) at most of the investigated sites. The mean PBOA chemical profile is clearly dominated by contribution from OM (78±9 % of the mass of the PBOA PMF on average), and only a minor contribution from the dust class (3±4 %), suggesting that ambient polyols are most likely associated with biological particle emissions (e.g., active spore discharge) rather than soil dust resuspension.