The most conventional and abundant tracers of biomass combustion in aerosol particles include potassium and biomarkers derived from thermally altered cellulose/hemicellulose (anhydrosugars) and lignin (methoxyphenols). However, little is known of the role biomass combustion plays as a particulate source of major plant polymers to the atmosphere. Here, concentrations of solvent-extractable anhydrosugars and methoxyphenols are compared to the yields of polymeric lignin oxidation products (LOPs) during a smoke plume event in Houston, Texas. Downwind aerosol samples (PM2.5) were collected surrounding a two-day wildfire in the McFaddin National Wildlife Refuge, 125 km southeast of Houston, which was 12–16 h directly downwind during the peak of the burn. Concentrations of all organic markers, potassium, and calcium increased by a factor of 2–13 within 1–2 days of the start of the fire and dropped to prefire levels 3 days after the peak event. Source signatures of anhydrosugars and methoxyphenols during the peak of the plume were identical to those of grass charcoals collected from the site, confirming the use of charcoals as end-members for source input reconstruction during atmospheric transport. An enrichment factor of 20 in the anhydrosugar to methoxyphenol ratio of aerosols versus charcoals can be explained partially by differences in degradation rate constants between the biomarker groups. LOPs comprised 73–91% of all lignin material in the aerosols, pointing to fires as major sources of primary biogenic aerosol particles in which lignin phenols occur predominantly in polymeric form.