Amendments, such as biochar, compost, and iron grit, used in phytostabilization studies, showed positive effects on soil physico-chemical properties, plant growth, and the microbial community. However, assisted phytostabilization studies do not always focus on the rhizosphere area where soil, plants, and microorganisms are affected by the amendments and plants and microorganisms can also interact with each other. The aims of this study were to evaluate the effects of amendment application on the exudation of organic acids by Salix viminalis plant roots, as well as the effects of amendments and plant development on the soil CHNS contents and the microbial community activity and diversity, assessed by measuring enzyme activities and using Biolog EcoPlatesTM tests and next-generation sequencing analyses. The results of the mesocosm experiment showed that soil C, H, and N contents were increased by amendment application, especially biochar and compost, while the one of S decreased. Enzyme activities, microbial activity, and diversity were also increased by the addition of amendments, except iron grit alone. Finally, the quantity of organic acids exuded by roots were little affected by amendments, which could in part explain the reduced effect of plant development on soil chemical and microbiological parameters. In conclusion, this study showed in particular that biochar and compost were beneficial for the soil CHN contents and the microbial community while affecting poorly Salix viminalis root exudates.