The incorporation of silica fume provides the solution to solve the low silica content of municipal solid waste incinerator fly ash, which hinders its utilisation in manufacturing alkali-activated solid waste incinerator fly ash. This paper reported the effect of silica fume and sodium silicate nature on the hardened properties, including compressive strength, hydration product and microstructure of alkali-activated municipal solid waste incinerator fly ash. In addition to characterising the property of municipal fly ash, the effect of silica fume in compressive strength of alkali-activated municipal solid waste incinerator fly ash under different sodium silicate dosage and modulus was investigated and its hydration products were determined by XRD and SEM. The results demonstrated that adding silica fume significantly improved the compressive strength by promoting the formation of C–S–H hydration product. Moreover, a higher sodium silicate content and modulus resulted in a higher compressive strength. The concentration of leachable heavy metals from harden specimen with 10% SF specimen was significantly reduced to the value which is much lower than the recommendation from Chinese standards.