Despite the progress in understanding heavy metals behavior during coal combustion, mitigation of heavy metals emissions is still a tough challenge due to a complex character of this phenomenon. Several lists of potentially toxic elements have been presented; in most cases, Pb belongs to the elements with the greatest environmental and human-health concern. The review paper is focused upon the behavior of Pb during coal combustion. with particular attention paid to decreasing its emissions. It summarizes the dominant parameters affecting its redistribution among coal combustion streams. As gaseous emissions can quite easily pass through the particulate control device, attention was paid primarily to Pb distribution between condensed and volatilized phases. A crucial factor enhancing Pb volatility is the presence of organic or inorganic chlorides, which is discussed in detail, including their chlorination mechanisms and interactions with other fuel/flue gas species. Components decreasing Pb volatility and promoting the formation of condensed phases are also discussed (higher levels of moisture, Na, O2 etc.). Factors enhancing Pb volatility, as well as factors facilitating Pb retention, are discussed with the view of fluidized-bed combustion, pulverized-fuel combustion, or co-combustion of coal with wastes.