To reveal the enrichment conditions and resource potential of coal-rock gas in the Ordos Basin, this paper presents a systematic research on the sedimentary environment, distribution, physical properties, reservoir characteristics, gas-bearing characteristics and gas accumulation play of deep coals. The results show that thick coals are widely distributed in the Carboniferous–Permian of the Ordos Basin. The main coal seams Carboniferous 5# and Permian 8# in the Carboniferous–Permian have strong hydrocarbon generation capacity and high thermal evolution degree, which provide abundant materials for the formation of coal-rock gas. Deep coal reservoirs have good physical properties, especially porosity and permeability. Coal seams Carboniferous 5# and Permian 8# exhibit the average porosity of 4.1% and 6.4%, and the average permeability of 8.7×10−3 μm2 and 15.7×10−3 μm2, respectively. Cleats and fissures are developed in the coals, and together with the micropores, constitute the main storage space. With the increase of evolution degree, the micropore volume tends to increase. The development degree of cleats and fissures has a great impact on permeability. The coal reservoirs and their industrial compositions exhibit significantly heterogeneous distribution in the vertical direction. The bright coal seam, which is in the middle and upper section, less affected by ash filling compared with the lower section, and contains well-developed pores and fissures, is a high-quality reservoir interval. The deep coals present good gas-bearing characteristics in Ordos Basin, with the gas content of 7.5–20.0 m3/t, and the proportion of free gas (greater than 10%, mostly 11.0%–55.1%) in coal-rock gas significantly higher than that in shallow coals. The enrichment degree of free gas in deep coals is controlled by the number of macropores and microfractures. The coal rock pressure testing shows that the coal-limestone and coal-mudstone combinations for gas accumulation have good sealing capacity, and the mudstone/limestone (roof)-coal-mudstone (floor) combination generally indicates high coal-rock gas values. The coal-rock gas resources in the Ordos Basin were preliminarily estimated by the volume method to be 22.38×1012 m3, and the main coal-rock gas prospects in the Ordos Basin were defined. In the central-east of the Ordos Basin, Wushenqi, Hengshan–Suide, Yan'an, Zichang, and Yichuan are coal-rock gas prospects for the coal seam #8 of the Benxi Formation, and Linxian West, Mizhi, Yichuan–Huangling, Yulin, and Wushenqi–Hengshan are coal-rock gas prospects for the coal seam #5 of the Shanxi Formation, which are expected to become new areas for increased gas reserves and production.