Polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/F) are highly bioavailable in humans, either through direct inhalation or indirectly by trophic transfer from contaminated food or water. The main sources of pollution with PCDD/F include industrial and non-industrial combustion sources, like domestic contaminated wood burning, house fires, burning of leaves from trees, etc. When looking for alternative energy sources and reduced energy costs, solid waste incineration plants are intended to be built in the vicinity of urbanized areas, and thus, the need emerges for examination and prediction of to what extent the solid waste incineration plants might affect the surrounding ecosystem, air pollution, and human health. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (or simply PCDD/F congeners) belong to the group of semi-volatile organic compounds with environmental stability and long-range transfer in the ambient air. Dioxin isomers are highly toxic and may have carcinogenic and mutagenic effects in humans. PCDD/F is detected in air, water, sediment, plants and animals. PCDD/F is generally distributed in the particulate phase in ambient air. For solid waste incineration plant emissions, the distribution of PCDD/F particles into particles with a diameter of <10 μm is more than 81% of the total particulate matter, and more than 54% of the PCDD/F is distributed into particles with a diameter of <2.5 μm. The aim of this study is to investigate the sources of PCDD/F, emissions and potential hazards, i.e., a toxic equivalent in Lithuania. The measurements were performed in two largest cities of Lithuania Vilnius and Kaunas, where the level of PCDD/F discovered was from 0.015 to 0.52 pg/m3 and from 0.02 to 0.05 pg/m3, respectively. The sites for the monitoring were selected based on their proximity to the locations of the planned cogeneration power plants in these cities.