During the cokemaking process, a significant amount of mercury occurring in a coal blend is released to the atmosphere. One of the ways of reducing this emission is to reduce mercury content in a coal blend. This could be obtained through the coal washing process. The optimization of this process requires the knowledge of mercury occurrence in coal, especially in its inorganic constituents. A qualitative analysis of mercury occurrence in the inorganic constituents of Polish coking coals was performed using an electron probe microanalyzer (EPMA). For that purpose, selected samples of rejects and middling products derived from the washing process in dense media separators and jig concentrators were examined. The obtained results have confirmed a strong connection between mercury occurrence and the presence of sulfides (pyrite, marcasite, and chalcopyrite) in Polish coking coals. Significant amounts of mercury were also noticed for barite, siderite, and aluminosilicates. The highest value of mercury content, at the level of 0.100%, was obtained for marcasite. For the analyzed coals, the effectiveness of mercury removal in the washing process was determined by the forms of pyrite occurring in coal. The highest values of effectiveness of mercury removal were obtained in the case of coals for which the large framboidal pyrite aggregates with chalcopyrite overgrowths were noticed. It was also found that middling products were characterized by the occurrence of the Hg-rich overgrowths of pyrite on organic matter. To achieve a significant reduction in mercury content in clean coal, it is necessary to develop an effective method of removing this form of pyrite from hard coal.