Mine soils often contain metal(loid)s that may lead to serious environmental problems. Phytoremediation, consisting in covering the soil with specific plants with the possible addition of amendments, represents an interesting way of enhancing the quality of mine soils by retaining contaminants and reducing soil erosion. In order to study the effect of an assisted phytoremediation (with willow and ryegrass) on the properties of soil pore water (SPW), we investigated the impact of amendment with biochar (BC) combined with the planting of willow and ryegrass on the behavior of several metal(loid)s (Pb, Zn, Ba, As, and Cd) in a mine soil. Data on the physicochemical parameters and concentrations of the different metal(loid)s in both SPW and in plant tissues of willow and ryegrass highlight the importance of BC for SPW properties in terms of reductions in soluble concentrations of Pb and Zn, although there was no effect on the behavior of As and Cd. BC also increased soluble concentrations of Ba, probably related to ion release by the BC. By improving major ions available in mine soil, BC improved the lifetime of plants and enhanced their growth. Plant development did not appear to significantly affect the physicochemical parameters of SPW. Willow and ryegrass growing on soil with BC incorporated Cd and Ba into their tissues. The influence of plants on the behavior of metal(loid)s was noticeable only for ryegrass growing in soil with 2% BC, where it modified the behavior of Pb and Ba.