A coke oven battery is not considered as a significant source of PCDDs/PCDFs emissions; however, due to small amounts of chlorine in coal dioxins, dibenzofurans may be formed. The paper presents the attempts to determine the level of emission of PCDDs/PCDFs from the COB underfiring system and to confront the obtained results with the calculations based on the mass balance of chlorine in the coking process and reactions of both chlorophenols formation and PCDDs and PCDFs formation from mono- and polychlorophenols. There were PCDDs/PCDFs concentrations measured in flue gases from the underfiring system of two COBs at a Polish coking plant. The measurements included both an old and a new battery. The obtained concentrations of PCDDs/PCDFs were lower than reported in the literature (0.5-1.7 ng I-TEQ/tcoke), while the results for old COB were on average 3 times higher than for the new one. It was found that PCDD/F emission from COB underfiring system is insignificant and that PCDDs/PCDFs formation during coal coking should consider the mechanisms of their formation from mono- and polychlorophenols, as well as the influence of process parameters on the synthesis.