In order to minimize emission of polychlorinated dibenzo dioxins and polychlorinated dibenzo furaris (PCDD/PCDFs) from municipal solid waste incinerators, it is important to maintain optimized operating conditions along with the system modification/improvement. Operating conditions of MSW incinerator make very complicated influence on formation of PCDD/PCDFs in each unit apparatus. For revealing these influences, concentrations of PCDD/PCDFs are measured from the stack and from the fly ash, while monitoring the plant operating conditions. The effects are grouped into 3 main categories, combustion conditions, de Novo synthesis effects, and adsorption/destruction effects in the flue gas treatment system. Interpretation of the results showed that de Novo synthesis effect, reformation by metalic catalyst, especially Cu in fly ash in the temperature range of 250∼500℃, is found to influence most dominantly on the concentration of PCDD/PCDFs. A plausible mathematical model for predicting