Disposal of significant amounts of dredged contaminated sediment poses an economic and environmental problem worldwide. Transforming contaminated sediment into value-added construction materials using low carbon MgO cement is a sustainable option; however, the weak mechanical strength and unreliable water solubility of MgO cement restrict its practical engineering applications. This study elucidates the potential role of industrial Si-rich minerals in the performance enhancement of MgO-based products via the promotion of magnesium silicate hydrate (M-S-H) gel formation. Quantitative X-ray diffraction and Si-29 nuclear magnetic resonance analyses indicated that compositions and crystallinities of the Si-rich minerals significantly influence the formation and polymerisation of the M-S-H gel. Pulverised fly ash was found to be a promising Si-rich mineral for generating polymeric M-S-H gel, whereas incinerated sewage sludge ash samples demonstrated a low degree of polymerisation, and the use of glass powder samples gave a low yield of M-S-H. The formation of M-S-H gel enhanced the compressive strength and water resistance (strength retention after water immersion). Further experiments demonstrated that Si-modified MgO cement can transform dredged sediment into fill materials with satisfactory mechanical properties and contaminant immobilisation. Therefore, the synergy between reactive MgO and Si-rich industrial waste is a novel option for sustainable remediation and environmental applications.