The role of chlorination reactions in the formation of polychlorinated dibenzofurans (PCDFs) in a municipal waste incinerator was assessed using a chlorination model for predicting PCDF isomer distributions. Complete distributions of PCDF congeners were obtained from a stoker-type municipal waste incinerator operated under 13 test conditions. Samples were collected from the flue gas prior to the gas cleaning system. While total PCDF yields varied by a factor of five to six, the distributions of congeners were similar. A chlorination model, dependent only on the observed distribution of monochlorinated isomers, was developed to predict the distributions of poly-chlorinated isomers formed by chlorination of dibenzofuran (DF). Agreement between predicted and measured PCDF isomer distributions was high for all homologues, supporting the hypothesis that DF chlorination can play an important role in the formation of PCDF byproducts.