In this work, the findings of the first assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in emissions releases to the atmosphere from coal-fired power plants are given. A total of five plants were selected for the study located at different provinces in Spain. In all the cases, the results revealed very low levels, in the range of 0.41 pg I-TEQ/Nm(3). The profile indicated in the majority of the cases predominance of highly chlorinated congeners being OCDD the most important contributor. The findings were also used to estimate contribution of PCDDs/PCDFs emitted from coal-fired power plants in Spain. Individual plant results revealed values below 0.02 g I-TEQ per year and plant. Nevertheless, considering the total coal consumption in Spain in 1997, the values are comparable to those reported in other countries in the range of 0.6-0.7 g I-TEQ per year. Moreover, emission factors were determined considering operating conditions of evaluated plants. In general, large variability was observed and values below 1-5 pg I-TEQ/kg coal were early reached.