With the rapid development of urbanization and the economy, the amount of municipal solid waste incineration fly ash (MSWI fly ash) dramatically increases and stacks up. Declining the leaching concentration of hazardous heavy metals in municipal solid waste incineration fly ash and enlarging the application range in wastewater and biosorption of non-sintered LWAs have always got more attention from more and more researchers. Green and non-sintered LWAs were prepared by using the waste solids (MSWI fly ash and coal fly ash) as raw materials through autoclave technology. In the meantime, the effect of severe leaching environment (pH = 1, 3, 5 and 7) on the stabilization of heavy metals in the LWAs with MSWI fly ash and extra heavy metals were systematically investigated by means of Inductively Coupled Plasma Optical Emission Spectrometer, X-ray diffraction, Fourier Transform Infrared Spectrometer, X-ray photoelectron spectra and Scanning electron microscope. The results revealed that the heavy metals are well immobilized in the LWA matrix through physical encapsulation and adsorption by hydration products (C-S-H). The leaching rate (LR) and cumulative leaching rate (CLR) of heavy metals, phase compositions and chemical structures in LWAs with heavy metals at pH of 1 are significantly changed, but the cumulative leaching rate of Pb2+ is lower than that of Zn2+ and Cu2+. The structure of hydration products in the matrix will be broken and reformed to gypsum under an acid environment (pH = 1). The leaching rate and cumulative leaching rate of heavy metals in LWAs with heavy metals under various leaching environments are much lower when the pH is above 1, which could meet the leaching requirement. This research could provide theoretical support for the application of non-sintered and municipal solid waste incineration fly ash based LWAs in concrete.