In recent years, woody plants have been widely utilized for the remediation of heavy metal tailings due to their large biomass and well-developed root systems. Among them, species like Nerium oleander, Koelreuteria paniculata, and Paulownia have demonstrated strong resistance and effective enrichment under lead and zinc stress. However, the precise impacts on the rhizosphere environment of slag remain unclear. This study employed slag from a lead-zinc mining region in Chenzhou City, Hunan Province, as the experimental substrate. Two control groups were established: 100% slag (CK group) and 90% slag + 5% mushroom residue + 5% calcium carbonate (S0 group). Additionally, Nerium oleander, Koelreuteria paniculata, and Paulownia were cultivated on the basis of the S0 group (S1 group). The study aimed to discern differences in substrate physicochemical properties, forms of Pb and Zn, volatile organic compounds, microbial community structure, and related indicators to explore the response mechanism of woody tolerant plants in the rhizosphere under lead and zinc stress. The findings revealed the following outcomes: Under enhanced conditions, these three plant species adjusted the slag substrate""s acid-base balance and enhanced water and nutrient retention by regulating parameters such as substrate pH, organic matter content, cation exchange capacity, available nitrogen, and available phosphorus. As a result, the effective content of Pb and Zn decreased by 16.29% to 36.50% and 24.50% to 47.33%, respectively. Furthermore, there was an increase in the abundance of organic compounds such as esters and phenols. The relative abundance of Proteobacteria decreased, while the abundance of genera in Bacteroidea, Actinobacteria, and Bradyrhizobium increased. In conclusion, planting woody plants under enhanced conditions not only altered the physicochemical properties of the substrate and the abundance of organic matter but also affected the structure of the microbial community. This led to an improved slag environment and a reduced bioavailability of Pb and Zn.