Siderite is a common carbonate mineral in coal and usually contains geochemical indications (elemental associations and isotopic compositions) for sedimentary environments and regional geological history, but the origin and enrichment mechanism of geochemically-pure siderite in coal is not fully understood. A better understanding of siderite origin in coal can help to decipher the depositional environment of peat and related geological processes of rank advances and epigenesis. This paper analyzed the petrological, mineralogical, and geochemical characteristics, particularly the content, occurrence, and origins of siderite in the Middle Jurassic coal from the Hexi mine of the Shenfu mining area, Ordos Basin, using optical microscopy, field emission-scanning electron microscopy, X-ray fluorescence, X-ray diffraction, inductively coupled plasma mass spectrometry, and isotope ratio mass spectrometry. The results indicate that the No. 4 Coal is rich in inertinite and is defined as an ultra-low to low sulfur, high volatile bituminous coal. Siderite has contents varying from 5.8% to 54.4% (low temperature ash basis) and occurs in radial or concentric circle nodules in the coal and is mainly distributed within the clay matrix. Syngenetic siderite in the Hexi coals is relatively pure in chemical compositions, and was formed in a brackish water environment affected by salt lakes under arid conditions. The high content of inertinite, high Sr/ Cu value, and positive Ce anomaly at the uppermost of the coal seam indicate that the escalating intensification of oxidation and evaporation. The Al2O3/TiO2 ratio and the diagrams of Al2O3/TiO2 vs. Zr/ TiO2 and Al2O3/TiO2 vs. Nb/Yb indicate that the sedimentary source rock in the study area is primarily intermediate-felsic. The delta 13CPDB-delta 18OSMOW diagram shows C and O for the siderite formation in this study were derived from marine carbonate rock alteration of the underlying Ordovician marine carbonate rock basement. The distribution patterns of rare earth elements and Y (Middle-type enrichment and Gd anomalies) in the coal further verify this hypothesis. Furthermore, siderite in the coal exhibits an enrichment in 13C suggest that bacterial fermentation of organic matter as another possible source of CO2. The iron of the siderite in the study coal was probably derived from the leaching of the magnetite-bearing granite.