The upper Permian Longtan Formation is widely distributed in southwestern China and is well known for multilayer coal and high organic shale, with significant shale gas potential that has yet to be fully explored and developed. The Longtan coal-bearing strata are composed of complex lithological assemblages of finegrained sedimentary rocks such as sandstone, coal, shale, and limestone, which exhibit significant differences from marine shale. To better understand the organic-rich lithofacies, their distribution, and their controlling factors, this study carried out a detailed survey of the outcrop and drill cores in the western Guizhou region and examined the fine-grained lithofacies, their assemblages, and their geochemical characteristics. The results showed that (1) the total organic carbon of the Longtan Formation shale in western Guizhou ranged from 1.44 to 14.79%, with an average of 6.41%, and the organic matter was mainly composed of vitrinite. The mineral composition was mainly clay minerals and brittle minerals; the clay minerals were mainly composed of kaolinite (average 11.13%) and illite/smectite mixed layers (average 26.69%) and the brittle minerals were mainly composed of quartz (average 31.63%) and feldspar (average 12.88%). (2) Eight types of lithofacies were identified, including silty mudstone, muddy siltstone, carbonaceous mudstone, carbonaceous shale, bioclastic-bearing mudstone, bioclastic-bearing sandstone, fine sandstone, and coal seam. (3) The six typical lithofacies assemblages were developed in the Longtan Formation, which represented different sedimentary environments of the marine−continental transitional facies in the study area. The lithofacies assemblages A and C represent sedimentation in the lagoon environment. The lithofacies assemblage B represents peat swamp facies. The lithofacies assemblage D represents a tidal flat facies peat flat-mixed flat-sand flat sedimentary environment. The lithofacies assemblage E and F represent the delta sedimentary environment. (4) The sedimentary model of the Longtan Formation in western Guizhou was predominantly deltaic and tidal flat sedimentary systems. Lithological and lithofacies studies of Longtan fine-grained rocks were used to provide a geological framework for examining the fine grain deposition distribution and shale gas resource evaluation. This study is highly important for understanding the sedimentology and oil and gas exploration in the region, providing a basis for identifying and exploring coal-bearing shale gas potential and a reference for the analysis of shale in the world's continental transitional areas.