The Yimin Ge-coal deposit, located in the Yimin coalfield, Inner Mongolia, is the third largest Ge-rich coal deposit in China just after the Lincang and Wulantuga Ge-coal deposits. Based on the coal and non-coal samples recently collected from the Wumuchang coal mining district in the Yimin Ge-coal deposit, this paper reports some new data on the mineralogical and geochemical characteristics of the Yimin high-Ge coals, and provides some new evidence for the possible mode of Ge enrichment in the Yimin coals. Mineralogical analyses were performed by means of Powder X-ray diffraction (XRD). Major and trace element concentrations were determined by inductively coupled plasma atomic-emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS), respectively. Element affinities were determined by Pearson correlation analysis. The studied coals fall within the coal rank between sub-bituminous A and high volatile bituminous C, with relatively high moisture content, high volatile matter yield and low to medium ash yield. Quartz and kaolinite are the main mineral matter in the Yimin coals, with small amounts of pyrite and traces of microcline. Common pyrite and As-bearing pyrite occurring in the Yimin coals show an epigenetic origin. The epigenetic precipitation of kaolinite, quartz and As-rich pyrite (with Ge, and other trace elements) in the Yimin coal fractures may be caused by activities of both hydrothermal and low temperature fluids. Compared to common Chinese and worldwide coals, the Yimin coals are markedly enriched in Ge (43 mg/kg), As (155 mg/kg), W (9.84 mg/kg) and slightly enriched in Pb (22 mg/kg), and Hg (0.24 mg/kg). Most of the elements (e.g. Al, K, Sc, Ti, V, Cu, Ga, Sn, Th and REEs) in the studied coals present an aluminosilicate affinity as deduced from their obvious positive correlation with Al and ash yields. High correlation coefficients of As, Hg, with Fe and S indicate a sulfide affinity of these elements in the Yimin coals. Germanium, B, Mo, and W in the studied coals show an organic affinity and a partial sulfur affinity as deduced from their negative correlation with Al and positive correlation with S, respectively. The preliminary and possible model for Ge enrichment in the Yimin Ge-coal deposit was that Ge was carried by hydrothermal fluids and then these fluids were incorporated in the water existing in the upper porous conglomerates and percolate in the top of the coal seam, where Ge was trapped by organic matter and finally enriched in an early diagenetic stage (humification-gelification).