Fine particle matter with aerodynamic diameter <2.5 microm (PM2.5) and gas-phase emissions from open burning of six fine (foliar) fuels common to fire-prone U.S. ecosystems are investigated. PM2.5 distribution is unimodal within the 10-450 nm range, indicative of an accumulation mode. Smoldering relative to flaming combustion shows smaller particle number density per unit time and median size. Over 100 individual organic compounds in the primarily carbonaceous (>70% by mass) PM2.5 are chemically speciated by gas chromatography/mass spectrometry. Expressed as a percent of PM2.5 mass, emission ranges by organic compound class are as follows: n-alkane (0.1-2%), polycyclic aromatic hydrocarbon (PAH) (0.02-0.2%), n-alkanoic acid (1-3%), n-alkanedioic acid (0.06-0.3%), n-alkenoic acid (0.3-3%), resin acid (0.5-6%), triterpenoid (0.2-0.5%), methoxyphenol (0.5-3%), and phytosterol (0.2-0.6%). A molecular tracer of biomass combustion, the sugar levoglucosan is abundant and constitutes a remarkably narrow PM2.5 mass range (2.8-3.6%). Organic chemical signatures in PM2.5 from open combustion of fine fuels differ with those of residential wood combustion and other related sources, making them functional for source-receptor modeling of PM. Inorganic matter [PM2.5 - (organic compounds + elemental carbon)] on average is estimated to make up 8% of the PM2.5. Wavelength dispersive X-ray fluorescence spectroscopy and ion chromatography identify 3% of PM2.5 as elements and water-soluble ions, respectively. Compared with residential wood burning, the PM2.5 of fine fuel combustion is nitrate enriched but shows lower potassium levels. Gas-phase C2-C13 hydrocarbon and C2-C9 carbonyl emissions are speciated by respective EPA Methods T0-15 and T0-11A. They comprise mainly low molecular weight C2-C3 compounds and hazardous air pollutants (48 wt % of total quantified volatile organic carbon).