Heavy metals (Pb, Cd, Ni, Co, Fe, Zn, Cr, As, Ag, platinum group, etc.) in trace amounts are natural components of the environment. However, their presence in excess may cause a serious threat to the stability of the ecosystem by inducing a drastic change in the quality and yield of crop products. Heavy metal toxicity in the agro-ecosystem has now become a major challenge for the planet. To increase crop productivity, it is necessary to evolve efficient, low-cost technologies for reducing metal toxicity. Many appropriate technologies are available for removing or reducing such toxicants but as a cost-effective, eco-friendly, and sustainable method—phytoremediation is gaining worldwide attention for its effectiveness. In the present book chapter, we attempt an overview of current knowledge on the roles of several species of plants from the family Brassicaceae as metal hyper-accumulators. Characteristics of plant species of Brassicaceae as phytoremediators of heavy metals, detailed mechanisms of phytoremediation by plants from the Brassicaceae family, and methods to enhance heavy metal phytoextraction by using chelating chemicals or through biotechnology and genetic engineering have been focused.