To understand the effect of leaf-surface pesticides on emissions of PCDD/F during biomass burns, nine combustion experiments simulating the open burning of biomass were conducted. Needles and branches of Pinus taeda (Loblolly pine) were sprayed with the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) at 1 and 10 times the manufacturer’s recommended application concentration. The biomass was then dried overnight, burned in an open burn test facility, and emission samples were collected, analyzed, and compared against emission samples from burning untreated biomass. Blank tests and analysis of PCDD/F in the raw biomass were also performed. Emission results from burning a water-sprayed control show a ∼20-fold increase in PCDD/F levels above that of the raw biomass alone, implicating combustive formation versus simple volatilization. Results from burns of pine branches sprayed with pesticide showed a statistically significant increase in the PCDD/F TEQ emissions when burning biomass at ten times the recommended pesticide concentration (from 0.22 to 1.14 ng TEQ/kg carbon burned (Cb), both ND = 0). Similarly, a 150-fold increase in the total PCDD/F congener mass (tetra- to octa-chlorinated D/F) above that of the control was observed (from 52 to 7800 ng/kg Cb), confirming combustive formation of PCDD/F from 2,4-D. More replicate testing is needed to evaluate effects at lower pesticide concentrations.