Biochar application has attracted great attention due to its diverse uses and benefits in the fields of environmental management and agriculture. Biochar modifies the composition of dissolved organic matter (DOM) in soil, which directly or indirectly controls the mobility of metal contaminants and their bioaccumulation. In this study, ten different hydrothermal biochars pyrolysed from mushroom waste (MSBC), soybean straw (SBBC), sewage sludge (SSBC), peanut shells (PNBC) and rice straw (RSBC) at two pyrolysis temperatures (200°C and 350°C) were used to investigate DOM changes in soil solution and their effects on metal availability and bioaccumulation. Biochar induced modification of soil DOM which was characterized by spectroscopic analysis of water soluble organic carbon, specific absorbance (SUVA254), UV–vis absorption, spectral slope (SR) and the absorption coefficient. Regarding rice plant growth, the biochar effects on biomass were greatly varied. Biochars (except for RSBC and MSBC) prepared at high temperature significantly (P≤0.05) suppressed the availability of As and Cd in soil and their subsequent bioaccumulation in rice plants. The highest reduction (88%) in bioaccumulated As was observed in rice grown on soil amended with SBBC prepared at 350°C (the highest temperature for hydrothermal technique). The addition of biochars (except RSBC and MSBC) prepared at high temperature markedly (p<0.05) decreased AsIII (30–92%), while the effects on dimethylarsenic acid (DMA) and arsenate (AsV) concentrations were not significant except for SSBC350 (prepared at 350°C) treatment. These results highlight the potential of biochar-DOM interactions as an important mechanism for suppressing the mobility and bioaccumulation of As and Cd in biochar-amended paddy agricultural systems.