The correlation between the content and morphology of Fe 2 O 3 and the yields of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied in this work. Three fly ash surrogates containing 1%, 2.5%, and 4% of Fe 2 O 3 were prepared and their effects on PCDD/Fs formation were investigated and compared to our previously studied 5% iron oxide sample using 2-monochlorophenol precursor model. As the intermediate of PCCD/Fs, environmentally persistent free radical formation propensity was correlated with the PCDD/Fs formation yields for different iron oxide samples. PCDD/Fs yield increases exponentially with the increasing iron content under pyrolytic conditions. On the contrary, low iron oxide content promotes oxidation and lowers yields of PCDD/Fs. Changing iron oxide clusters morphology (crystallinity and cluster size) affects the mechanism of PCDD/Fs formation-on larger crystallites, a bidentate chemisorption of precursor is preferred leading to lower chlorinated congeners, while smaller clusters promote formation of PCDFs through mixed monodentatebidentate surface species, resulting in formation of congeners with 1 chlorine more. This studies further confirm the propensity of iron oxide to predominantly form PCDFs. The iron content also defines PCDDs:PCDFs ratio.