The relationship between the properties of fly ash generated during waste incineration and the thermal formation of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs), was investigated on two artificial wastes using a laboratory incinerator. Fly ash particles were sampled in the post-combustion zone at approximately 300 degrees C and were characterized with the following complementary techniques: X-ray diffraction (XRD), scanning electron microscopy energy-dispersive X-ray (SEM-EDX), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. Flue gas samples were collected at the same location and analyzed for Mo-OCDDs, Mo-OCDFs, Tri-DCBs, and Di-OCNs. A strong correlation between fly ash characteristics and waste composition exists for several of the elements considered in this work. For instance, the waste containing the highest levels of Al produced more abundant Al-bearing minerals and elemental Al in the resulting fly ashes. Copper, an especially important POP formation catalyst, was not detected in the top 10 nm surface of fly ash particles but rather occurred within the top 2 pm, indicating that surface copper of catalytic importance for POP formation reactions was not available. Important contributions of ferric iron present in the abundant fly ash-building hematite phase could have also played an important role, especially given its documented contributions in chlorination pathways. Orthogonal projections to latent structures (OPLS) modeling resolved the relationship between fly ash properties and the post-combustion POP formation. These efforts showed that low levels of ash-forming elements (i.e., Na, Mg, Fe, Ti, etc.) were associated with an increase in flue gas S levels, which, in turn, poison the Cl-2 production via the Deacon process. Wastes with depleted levels of fly-ash-building elements should therefore be favored for minimizing PCDD, PCDF, PCB, and PCN release caused by incineration.