A pilot study was performed to evaluate formation, distribution and emission of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from cement kilns that co-process fly ash from municipal solid waste incineration (MSWI). Stack gas and particulate samples from multiple stages in the process were collected and analyzed for PCDD/Fs. Stack emissions of PCDD/Fs were below the European Union limit for cement kilns (0.1 ngTEQm(-3)). PCDD/F concentrations in particulates from the cyclone preheater outlet, suspension preheater boiler, humidifier tower, and back-end bag filter were much higher than in other samples, which suggests that these areas are the major sites of PCDD/F formation. Comparison of PCDD/F homolog and congener profiles from different stages suggested that tetra- and penta-chlorinated furans were mainly formed during cement kiln co-processing of MSWI fly ash. Three lower chlorinated furan congeners, including 2,3,7,8-tetrachlorodibenzofuran, 1,2,3,7,8-pentachlorodibenzo-p-dioxin and 2,3,4,7,8-pentachlorodibenzofuran, were identified as dominant contributors to the toxic equivalents (TEQ) of the PCDD/Fs. The concentration of PCDD/Fs in particulates was correlated with chloride content, which is consistent with its positive effect on PCDD/F formation. This could be mitigated by pretreating the feedstock to remove chloride and metals. Mass balance indicated that cement kilns eliminated about 94% of the PCDD/F TEQ input from the feedstock. (C) 2015 Elsevier B.V. All rights reserved.