Two typical types of electronic waste (E-waste) were selected to investigate the emission characteristics of polycyclic aromatic hydrocarbons (PAHs) during pyrolytic processing, including emission factor, compositional profile, size distribution and gas-particle partitioning. The mean emission factors (EFs) of total PAHs were measured to be 2.77 +/- 1.41 mu g/g and 23.65 +/- 14.52 mu g/g for printed wiring boards and plastic casings, respectively, lower than those for coal combustion and biomass burning. Low molecular weight species were predominant in exhaust fumes, with overwhelming amounts of naphthalene (NAP) and phenanthrene (PHE) in the gaseous phase and particulate phase, respectively. The particle-size distribution exhibited the largest enrichment of total PAHs in finer particles less than 2.1 mu m. Similarly, the distributions of individual species were dominated by finer particles. Most freshly emitted PAHs were liable to exist in particulate phase relative to gaseous phase. Based on the benzo[a]pyrene equivalent carcinogenic power, PAHs in particulate phase may have much stronger toxicity compared with those present in gaseous phase. The gas-particle partitioning behaviors of freshly emitted PAHs from pyrolytic processing of E-wastes were mainly regulated by absorption rather than adsorption, and the gas-particle partitioning did not reach equilibrium.