Municipal solid waste incineration (MSWI) fly ash is a by-product of garbage incineration power generation, and its disposal is currently a world problem because it contains over standard heavy metals. This research aims to solidify the heavy metals in MSWI fly ash and make it to be utilizable construction materials under the guidance of intermediate-calcium cementitious materials (ICCM), and meanwhile figure out the solidification and hydration mechanism. The hydration characteristics of ICCM were characterized by XRD, FTIR, ²⁹Si MAS-NMR and SEM techniques, and the environmental properties are investigated by TCLP and EPMA. The results indicate that the optimal ratio of (CaO+MgO)/(SiO₂+Al₂O₃) for ICCM is at the range of 0.76-0.88. The compressive strengths of ICCM reach the 42.5R normal Portland cement level, and the leaching concentrations of heavy metals meet the Chinese integrated wastewater discharge standard GB 8978-1996. As predominant hydration products, ettringite, hydrocalumite and amorphous C-S-H gel are principally responsible for the strength development of ICCM, and the (Ca+Mg)/(Si+Al) ratio at 0.88 has the best polymerized structure. The heavy metals are well solidified through combining with the C-S-H gel or absorbed in the hydration pastes. This paper provides an effective solution to use the MSWI fly ash in building material.