The immobilizing effects of wood biochar (BW2%) and iron grit (Z1%) applied alone or in combination (BW2% + Z1%) to agricultural (M750) and brownfield (MAZ) soils highly contaminated by metals were assessed in a greenhouse experiment. The results showed that Z1% and BW2% + Z1% were the most efficient amendments to reduce Cd, Cu, Pb, and Zn mobility, environmental availability, and phytoavailability in the M750 soil. The oxidation of Z1% allowed part of the Cu and Zn pools present in exchangeable or carbonate-bound forms (labile fraction) to complex in less mobile forms. In this soil, the metal chemical extractions (0.01 M CaCl2 and 0.05 M EDTA) and the DGT (diffusive gradient in thin films) devices to assess metal in soil solution and soil pore water (SPW) also highlighted the immobilizing characteristic of Z1%. In most cases, the addition of BW2% to Z1% (BW2% + Z1%) did not improve this effect, except for the dissolved Pb and Zn concentrations in the M750 soil solution. It was also observed that Cd, Pb, and Zn passed throughout DGT mimicking the biological cell membrane were reduced by all amendments of the M750 soil corroborating metal concentrations measured in rye grass shoots. In the MAZ soil, metals were less available as shown by their low extractability rate, low capacity of metal resupply from the solid phase to pore water, and low phytoavailability. The poor metal availability could be explained by the high levels of carbonate and organic matter contents in this soil. Nevertheless, a decrease of the Cu environmental availability and the Cu concentrations in rye grass shoots grown on the MAZ soil was also observed in the soil amended with Z1% alone or in combination with BW2%. From a health point of view, the most effective amendment to reduce human exposure through ingestion of soil particles for the M750 and MAZ soils was BW2% for Cd and BW2% + Z1% for Pb. However, the presence of rye grass minimized the amendments’ beneficial effects.