The addition of mineral-solubilizing microbial inoculums is a kind of biological measure for vegetation restoration of rock mining areas. Its function is to accelerate soil weathering, improve soil fertility, improve the ability of plants to fix soil. Through understanding the response of plant rhizosphere microbial community to the mineral-solubilizing microbial inoculums, it is helpful to popularize the use of mineral-solubilizing microbial inoculums. However, little is known about the changes of plant rhizosphere soil microbial communities after the addition of mineral-solubilizing microbial inoculums. Therefore, the purpose of this study was to reveal the pasthways through which different mineral-solubilizing microbial inoculums positively affect underground part of R. pseudoacacia. A pot experiment was conducted to investigate the responses of rhizosphere soil bacterial and fungal communities in R. pseudoacacia by taking 32 samples from four different mineral-solubilizing microbial inoculums treatments. The results showed that the effect of mineral-solubilizing microbial inoculums on the structure of fungal community was greater than that of bacterial community. But the relative abundance of Proteobacteria was increased, which had a strong positive correlation with root nodulation. In terms of microbial diversity, mineral-solubilizing microbial inoculums had a greater effect on the diversity and evenness of bacterial community. It is worth noting that correlation analysis showed that Proteobacteria and Verrucomicrobia in bacteria and Ascomycota and Zoopagomycota in fungi were positively correlated with soil enzyme activity and plant growth. RDA analysis showed that the relative abundance of these two phyla in bacteria also had positive effects on plant root nodulation. Our results showed that the addition of mineral-solubilizing microbial inoculums can optimize the rhizosphere soil microbial community structure, promote R. pseudoacacia root nodulation, and enhance the nitrogen fixation capacity of plants. In addition, this study can provide a theoretical basis for the application of mineral-solubilizing microbial inoculums to a wide range of slope ecological restoration.