The mining of manganese brings excellent wealth to humankind. However, it destroys the ecological environment, mainly manifested as heavy metal pollution and vegetation destruction. The restoration of ecological vegetation in manganese mining areas has become an important work after mineral exploitation. The effect of bryophytes on ecological restoration in mining areas is irreplaceable. The bryophytes diversity and its pioneering role in two types of manganese waste residue areas were investigated in Guizhou province, China. The results showed that there were 24 species of mosses in mine waste slag areas, and all of them belonged to 6 families and 15 genera; the species Gymnostomum subrigidulum, Pohlia gedeana, and Bryum atrovirens were the dominant mosses. There were 6 species of mosses in electrolytic manganese slag areas, and all of them belonged to 5 families and 5 genera. The dominant moss was B. atrovirens. The bryophytes diversity in the electrolytic manganese slag areas with lower pH was poorer than that in mine slag areas. The accumulation of heavy metals in mosses showed that B. atrovirens collected from two types of areas had a strong ability to accumulate Mn with the cumulants 5588.00 μg/g and 4283.41 μg/g, respectively. All mosses had a strong enrichment ability to Cd. It indicated that mosses had strong tolerance to heavy metals. Bryophytes increased the available nutrients and bacterial community diversity of mosses growth substrates in two types of areas. Besides, we studied the relationships between bacterial community structure and soil factors. The main soil factor affecting the bacterial community structure was available nitrogen (AN) in mine waste slag areas, while it was pH in the electrolytic manganese residue areas. The systematic study suggested that bryophytes increased the available nutrients and the microbial community diversity of the growth substrates in manganese waste residue areas, which provided the basic conditions for the growth of vascular plants.