A field study was conducted to determine the effects of ambient conditions and burning practices of rice fields in Taiwan on the chemical and physical characteristics of the smoke aerosol. Rice straw was burned on an actual rice field under typical conditions and smoke particles were collected immediately downwind of the field over the full particle size spectrum. Here we present size distributions of levoglucosan, a common molecular tracer for biomass burning, as well as detailed concentration patterns of three anhydrosugars, including mannosan, and galactosan, in addition to smoke aerosol concentrations of inorganic ions and carbonaceous species. The generated smoke aerosol was characterized by a high OC/EC ratio (10) and a large fraction of potassium (K+) and chloride (Cl-) ions at a Cl-/K+ ratio of 2. Levoglucosan showed a distinct bimodal distribution in the smoke particles with a large fraction (up to 56%) of the total levoglucosan mass observed in very large particles (PM 10). The prevailing ambient conditions (such as relatively high humidity), atmospheric processes (e.g., particle coagulation, hygroscopic growth, and deposition), the specific burning practices of rice fields in Taiwan (slow burning of straw spread in thin layers on the ground), as well as the inherent properties of rice straw likely influenced the particle size characteristics of the smoke tracer. Moreover, the relative abundance of the three biomass burning tracers showed a unique pattern (in good agreement with previous chamber burn measurements): levoglucosan-to-mannosan ratios were distinctly higher (with an average value of 27) than those observed for other types of biomass, such as softwood, hard wood, peat, or leaves, in previous studies. Such chemical fingerprint may be used in source apportionment studies for the assessment of contributions from the combustion of specific types of biomass.