Deep coalbed methane (CBM) demonstrates significant production potential, and a fervent exploration and development boom is currently underway in China. The permeability of coal reservoirs is heavily influenced by pore–fracture structure heterogeneity. Some researches have been conducted on deep coals’ pore–fracture structure; however, these studies mostly consider coal as a homogeneous material, neglecting the heterogeneity of the macrolithotypes within the coal. In this study, 33 deep coals with burial depths of more than 2000 m were obtained from the Daning-Jixian block of the Ordos Basin, covering all macrolithotypes: bright coal (BC), semi-bright coal (SBC), semi-dull coal (SDC), and dull coal (DC). These samples were subjected to three sets of NMR tests in dry, fully saturated, and irreducible water conditions, with the pore–fracture structure characteristics being analyzed. The results demonstrate that the sampled deep coals’ pore–fracture structure is highly heterogeneous, with transitional pores being dominant, followed by mesopores, “macropores and fractures”, and micropores. The NMR T2C ranges from 0.61 to 2.44 ms, with an average of 1.19 ms; a higher T2C value indicates more developed micropores. The ranges for producible water porosity (φpr) and producible water saturation (Spr) are 0.31–7.24% (avg. 2.42%) and 6.97–71.47% (avg. 31.06%), respectively. Both of them exhibit a high positive correlation with the total volumes of “macropores and fractures” and mesopores. Compared to SDC and DC, the BC and SBC, especially the former, overall contain more “macropores and fractures” and mesopores, fewer transitional pores and micropores, and higher φpr and Spr. These findings suggest that regions with abundant BC and SBC should be prioritized during deep CBM exploration and production due to the inherently superior permeability and gas extraction potential of BC and SBC, and these coals are likely to require less intensive stimulation to achieve higher recovery rates and could provide more sustainable gas production over time.