According to test data of proximate analysis, sulfur content and ash composition of a large number of Permian coals that sampled from 13 coal mines from Bijie city of Guizhou province, this paper provides an overall coal quality characteristic for Permian coal of Bijie city. On this basis, the correlation between sulfur and ash composition and coal formation environment was discussed in detail. The results show that Permian coal in Bijie region is characterized by extra-low total moisture, medium-high sulfur, medium ash yield (air dried basis) and extra-low volatile (air dried ash free basis), etc., as a whole belongs to anthracite coal. Coal formation environment could be explained by detailed study of sulfur distribution, different sulfur forms, ash yield distribution and its composition in coal. Vertical variety of sulfur content in main mineable coal seams from Bijie could clearly inverse twice main marine transgression and regression within the study region during late Permian, meanwhile horizontal distribution of sulfur content in coal is mainly characterized by “southeast high but northwest low”, which can be attributed to the progression of sea water from southeast to northwest. Analysis of sulfur forms indicates that organic sulfur in coal tends to account for only a small proportion, distinctly different from coal seams that formed in continental environment or shallow platform. In addition, analysis of ash yield, ash composition indicator and a Three Unit Method illustrates that during late Permian reducibility of coal formation environment in Bijie increased gradually from northwest to southeast, which is similar to the conclusion of sulfur mentioned above. Comprehensive analysis indicates that the types of coal formation environment in study area during late Permian were mainly delta distributary channels/bays, tide influenced lower delta plain, tidal flat and shallow lagoon, etc.. Sulfur content is high in coal seams formed in tidal flat or shallow lagoon that influenced strongly by sea water, but is relative low when coal seam was formed in delta environment, where sea water influence was weak. The main conclusions in this paper are similar to those based on lithofacies paleogeography and element geochemistry proposed by other scholars.