Emission from field burning of crop residue, a common practice in many parts of the world today, has potential effects on air quality, atmosphere and climate. This study provides a comprehensive size and compositional characterization of particulate matter (PM) emission from rice straw (RS) burning using both in situ experiments (11 spread field burning) and laboratory hood experiments (3 pile and 6 spread burning) that were conducted during 2003–2006 in Thailand. The carbon balance and emission ratio method was used to determine PM emission factors (EF) in the field experiments. The obtained EFs varied from field to hood experiments reflecting multiple factors affecting combustion and emission. In the hood experiments, EFs were found to be depending on the burning types (spread or pile), moisture content and the combustion efficiency. In addition, in the field experiments, burning rate and EF were also influenced by weather conditions, i.e. wind. Hood pile burning produced significantly higher EF (20±8 g kg−1 RS) than hood spread burning (4.7±2.2 g kg−1 RS). The majority of PM emitted from the field burning was PM2.5 with EF of 5.1±0.7 g m−2 or 8.3±2.7 g kg−1 RS burned. The coarse PM fraction (PM10-2.5) was mainly generated by fire attention activities and was relatively small, hence the resulting EF of PM10 (9.4±3.5 g kg−1 RS) was not significantly higher than PM2.5. PM size distribution was measured across 8 size ranges (from <0.4 μm to >9.0 μm). The largest fractions of PM, EC and OC were associated with PM1.1. The most significant components in PM2.5 and PM10 include OC, water soluble ions and levoglucosan. Relative abundance of some methoxyphenols (e.g., acetylsyringone), PAHs (e.g., fluoranthene and pyrene), organochlorine pesticides and PCBs may also serve as additional signatures for the PM emission. Presence of these toxic compounds in PM of burning smoke increases the potential toxic effects of the emission. For illustration, an estimation of the annual RS field burning in Thailand was made using the obtained in situ field burning EFs and preliminary burning activity data.