The present study experimented five biochars, one made from wood (400 °C, 12 h) and four made from miscanthus cultivated on contaminated soils (temperature 400/600 °C, duration 45/90 min). They were used as amendments at a 2% application rate on soil, cultivated or not cultivated with ryegrass, contaminated with (i) metals (Cd, Pb, and Zn), (ii) eight polycyclic aromatic hydrocarbons (PAHs), and (iii) a mix of metals and PAHs. The objectives were (i) to compare the effectiveness of the five biochars on soil parameters and pollutant availability and (ii) to determine the influence of soil multicontamination and ryegrass cultivation on biochar effectiveness. The results showed that biochar application did not necessarily lead to lower pollutant extractability and metal bioaccessibility. However, differences were highlighted between the biochars. The miscanthus biochars produced at 600 °C (BM600) showed higher effectiveness at decreasing metal extractability than the miscanthus biochars produced at 400 °C (BM400) due to its better sorption characteristics. In addition, ryegrass cultivation did not impact pollutant availability but modified metal bioaccessibility, especially for the soil amended with the BM600 and the woody biochar. Moreover, the presence of PAHs also negatively impacted the metal bioaccessibility in the soil amended with the BM600, and, on the contrary, positively impacted it in the soil amended with the BM400. Complementary studies are therefore necessary to understand the mechanisms involved, particularly in a context where soils requiring remediation operations are often multicontaminated and vegetated.