Burning of agricultural waste residue is a common method of disposal when preparing land following crop harvest. This practice introduces volatile organic compounds, including polycyclic aromatic hydrocarbons (PAHs), into the atmosphere. This study examines the particle size distribution in the smoke emissions of two common agricultural waste residues (biofuels) in California, almond prunings and rice straw. The residues were burned in a combustion chamber designed specifically for this purpose, and the smoke emissions were collected on 10-stage MOUDI impactors for analysis of PAH and total particle mass. The results, in units of emission factors, show that combustion temperature is an important factor in determining the smoke particle PAH composition. Total PAH emissions from rice straw burns were 18.6 mg kg−1 of fuel, while the emissions from almond prunings were lower at 8.03 mg kg−1. The less volatile five- and six-ring PAH was predominately on smaller particles where it condensed in the early stages of combustion while the more volatile three- and four-ring PAH formed on larger particles as the smoke cooled.