Heavy metal pollution due to mining activities poses a significant threat to agricultural production, ecosystem health, and food security in South Africa. This review integrates current knowledge on the use of mustard spinach (Brassica juncea (L.) Czern.) for the bioremediation of polluted water and soil, focusing on enhancing phytoremediation efficiency through the use of silicon-based biostimulant treatments. Mustard spinach is known for its capacity to accumulate and tolerate high levels of toxic metals, such as Pb, Cd, and Hg, owing to its strong physiological and biochemical defense mechanisms, including metal chelation, antioxidant activity, and osmotic adjustment. However, phytoremediation potential is often constrained by the negative impact of heavy metal stress on plant growth. Recent studies have shown that silicon-based biostimulants can alleviate metal toxicity by reducing metal bioavailability, increasing metal immobilization, and improving the antioxidative capacity and growth of plants. Combining silicon amendments with mustard spinach cultivation is a promising, eco-friendly approach to the remediation of mining-impacted soils and waters, potentially restoring agricultural productivity and reducing health risks to the resident populations. This review elucidates the multifaceted mechanisms by which silicon-enhanced phytoremediation operates, including soil chemistry modification, metal sequestration, antioxidant defense, and physiological resilience, while highlighting the practical, field-applicable benefits of this combined approach. Furthermore, it identifies urgent research priorities, such as field validation and the optimization of silicon application methods.