In order to ascertain the kaolinite crystallinity of Carboniferous Permian coal-measure kaolinite rocks, seven groups of fresh samples were collected from below the ground in the Xiaoyu mine, Datong coalfield. Microscopy, X-ray diffraction (XRD), differential thermal analysis (DTA), infrared (IR) spectroscopy and X-ray fluorescence (XRF) spectrometry methods were applied to the samples. The petrographic analysis results show that the kaolinite rocks are characterized as compact, phaneritic, clastic, sand-bearing, sandy and silty types; the kaolinite content in the Shanxi formation and upper Taiyuan formations was more than 95%, while it was 60–90% in the middle and lower Taiyuan formations. Based on the Hinckley index and the features of XRD, DTA and IR of kaolinites, crystallinity was classified as having three grades: ordered, slightly disordered and disordered. The kaolinites’ SiO₂/Al₂O₃ molar ratio was about 1.9–5.7, with a chemical index of alteration (CIA) of about 95.4–99.5. This research suggests that the kaolinite crystallinity correlates positively to its clay mineral content, purity and particle size, which are also related to the SiO₂/Al₂O₃ molar ratio and CIA. The original sedimentary environment and weathering have a direct influence on kaolinite crystallinity, and the existence of organic matter is conducive to the stable existence of kaolinite. The study results have significance for the extraction and utilization of coal-measure kaolinite and the development of kaolinite crystallography and mineralogy.