As a potential strategic mineral resource, lithium (Li) in coal measures (including coal and parting) has attracted increasing attention from scholars globally. For a long time, Li in coal measures has been studied mainly on the macro-scale (whole rock); however, the microscopic characteristics of Li and Li isotope variations in coal measures are less well known. In this study, the No. 6 coal measures in the Haerwusu Mine were studied using ICP-MS, XRD, SEM-EDS, MC-ICP-MS, and LA-ICP-MS. The geochemical and mineralogical characteristics, the microscale distribution of Li in minerals, and the Li isotopes of Li-rich coal and parting in the No. 6 coal measure were investigated. The results show that the Li content in the No. 6 coal seam ranges from 3.8 to 190 μg/g (average 83 μg/g), which is lower than the parting (290 μg/g) and higher than the comprehensive evaluation index of Li in Chinese coal (80 μg/g). LA-ICP-MS imaging showed that Li in the coal is mainly contained within cryptocrystalline or amorphous lamellae aluminosilicate materials, and the Li content in lenticular aggregate kaolinite is low. The Li in parting is mainly found in illite/chlorite. The δ7Li of the coals was 3.86‰, which may be influenced by the input of the source rock. The δ7Li of the parting (7.86‰), which was higher than that of the coal, in addition to being inherited from the source rock, was also attributed to the preferential adsorption of 7Li by the secondary clay minerals entrapped in the parting from water during diagenetic compaction. Finally, by integrating the peat bog sediment source composition, sedimentary environment evolution, and Li isotope fractionation mechanism of No. 6 coal, a Li metallogenic model in the Li-rich coal measure was initially established. In theory, the research results should enrich the overall understanding of the Li mineralization mechanism in coal measures from the micro-scale in situ and provide a scientific basis for the comprehensive utilization of coal measure resources.