Municipal solid waste incineration fly ash (MSWI FA) is categorized as a hazardous waste with significant implications on environmental safety and human health. This study tailored three types of alkali-activated materials (AAMs) by using ground granulated blast-furnace slag (GGBS) and metakaolin (MK) for the low-carbon stabilization/solidification (S/S) of MSWI FA. The intricate interactions between MSWI FA and AAMs synthesized from Al-rich precursors and Ca-rich precursors were investigated to elucidate the microstructural alterations of AAM-MSWI FA systems. Comprehensive characterization techniques were conducted, including isothermal calorimeter, thermal gravimetric analysis, Fourier-transform infrared (FTIR), X-ray diffraction (XRD), and ²⁷Al and ²⁹Si nuclear magnetic resonance (NMR). The results revealed that the incorporation of MSWI FA significantly delayed alkali activation reactions, hindering the formation of aluminosilicate gel due to high contents of Cl and potentially toxic elements (PTEs) in the MSWI FA. High volume of dissolved Cl from MSWI FA would react with available Ca from MSWI FA and GGBS as well as Al from GGBS and MK to form Friedel's salt, and this reaction was found to be more dominant in the Al-rich environment. Meanwhile, the C-(N-)A-S-H gel exhibited longer chain length in the Al-rich environment than in the Ca-rich environment. Overall, this study delivers microstructural insights into AAM-MSWI FA systems utilizing GGBS and MK as precursors. The results provide scientific groundwork for diverse practical applications of AAM-MSWI FA materials, thereby supporting the development of resource-efficient and low-carbon hazardous waste treatment strategies.