Silicon (Si) has been well documented to mitigate phytotoxicity of metals including manganese (Mn), iron (Fe), aluminium (Al), cadmium (Cd), arsenic (As), chromium (Cr), lead (Pb), copper (Cu) and zinc (Zn). However, the mechanisms explaining this phenomenon are still not clear. In general, there are two mechanisms, i.e. an external ( ex planta ) and an internal ( in planta ) one, proposed for explaining why and how Si can regulate plant resistance and/or tolerance to metal toxicity. Among the interactions of Si with metals, the possible roles of Si in enhancing tolerance to Mn and Al have been most extensively investigated, while over the last decade more work has been done on the Si-mediated alleviation of toxicity of the most important heavy metals, i.e. Cd, As, Cr and Pb. Nevertheless, direct evidence is still lacking that can clearly dissect the mechanisms involved in Si-mediated tolerance against metal toxicity, especially at the molecular level.