Mercury (Hg) is a toxic trace element emitted from coal conversion and utilization. Samples with different coal ranks and gangue from Ningwu Coalfield are selected and investigated in this study. For understanding dependence of mercury distribution characteristics on coalification degree, Pearson regression analysis coupled with Spearman rank correlation is employed to explore the relationship between mercury and sulfur, mercury and ash in coal, and sequential chemical extraction method is adopted to recognize the Hg speciation in the samples of coal and gangue. The measured results show that Hg is positively related to total sulfur content in coal and the affinity of Hg to different sulfur forms varies with the coalification degree. Organic sulfur has the biggest impact on Hg in peat, which becomes weak with increasing the coalification degree from lignite to bituminous coal. Sulfate sulfur is only related to Hg in peat or lignite as little content in coal. However, the Pearson linear correlation coefficients of Hg and pyritic sulfur are relatively high with 0.479 for lignite, 0.709 for sub-bituminous coal and 0.887 for bituminous coal. Hg is also related to ash content in coal, whose Pearson linear correlation coefficients are 0.504, 0.774 and 0.827 respectively, in lignite, sub-bituminous coal and bituminous coal. Furthermore, Hg distribution is directly depended on own speciation in coal. The total proportion of F2 + F3 + F4 is increased from 41.5% in peat to 87.4% in bituminous coal, but the average proportion of F5 is decreased from 56.8% in peat to 12.4% in bituminous coal. The above findings imply that both Hg and sulfur enrich in coal largely due to the migration from organic state to inorganic state with the increase of coalification degree in Ningwu Coalfield.