Vetiveria zizanioides L. is a Gramineae herbaceous perennial with rapid growth and is highly adaptable to its environment. It is often found in wasteland and lead/zinc mining abandoned soil. V. zizanioides is also strongly adaptable to copper mine tailings. The criteria for determining successful phytoremediation focus on both aboveground vegetation and substrate characterization. To understand the effects of artificial revegetation on the remediation of wastelands associated with the Tongling copper mine tailings in Anhui Province, we studied the dynamic changes in chemical properties, microbial biomass, enzyme activity in the tailings, and the relationships between these factors. The tailings were collected under V. zizanioides communities constructed on copper mine tailing wastelands at different times: JX (V. zizanioides communities were established in the recent stage); ZX (V. zizanioides communities were established in the middle stage); and OX (V. zizanioides communities were established in the early stage). The results showed that the tailings under the ZX and OX communities, had higher pH values and lower electrical conductivity and available Cu and Pb concentrations than the tailings under the JX community, indicating that the process of tailings acidification slowed down after the establishment of the V. zizanioides community. As the V. zizanioides community developed over time, the total N and available P in the tailings at 0-5 cm and 5-20 cm depths increased; with the total N and available P in the tailings at 0-5 cm under the OX 4.64 and 22.44 times higher, respectively than at the same depth under the JX. The total N accumulation at 0-5 cm was significantly higher than at the 5-20 cm depth, indicating the effect of the phytoremediation on improving the substrate chemical properties. With increased plantation time, the dehydrogenase, catalase and urease enzyme activities and the microbial biomass C and N contents also gradually increased at the 0-5 cm and 5-20 cm depths, but the alkaline phosphatase activity did not increase. The dehydrogenase and catalase activities and the microbial biomass C and N contents were all either extremely significantly or significantly negatively correlated with the electric conductivity. However, the microbial biomass N contents and all soil enzyme activities were significantly positively correlated to the total N content, indicating that total N was a dominant influence on soil enzyme activities. The microbial biomass and most soil enzyme activities decreased with increasing Cu and Pb contents, and the dehydrogenase and catalase activities were most sensitive to Cu, but less sensitive to Zn. The V. zizanioides has shown a significant ability to improve the chemical properties of tailings, and also to increase microbial biomass and soil enzyme activities. It is an adaptive plant species, and is recommended for the ecological rehabilitation of copper mine tailing wastelands.