Vitrification is a promising treatment for municipal solid waste incineration fly ash (MSWI-FA); however, high energy consumption due to the high MSWI-FA fusion temperature limits the development and application of this technique. In this study, fine slag ash (FSA) derived from coal gasification and coal gangue ash (CGA) were mixed with MSWI-FA to reduce the ash fusion temperature. The transformation of minerals in ash during thermal treatment was examined via X-ray diffraction and thermodynamic equilibrium calculations. The ash flow behaviour was observed using a thermal platform microscope, and the silicate structure was quantified using Raman spectra. The co-melting mechanisms for the mixed ash were systematically investigated. Results indicate that the flow temperature (FT) of the mixed ash exhibited an initial decrease and subsequent increase as a function of the addition ratio of FSA or CGA. Lowest ash FT of 1215 °C and 1223 °C were recorded for addition of 50% FSA and 50% CGA, respectively; further, these temperatures were lowered by > 285 °C and >277 °C respectively, relative to FT of the MSWI-FA. The transformation of minerals and silicate structure during mixed ash heating was responsible for the variation in the ash fusion temperature. CaO in MSWI-FA tended to react with mullite, quartz and haematite in FSA and CGA, forming minerals such as anorthite, gehlenite, and andradite with relatively low melting points. The addition of FSA or CGA caused changes in the silicate network structure of the mixed ash. In particular, 50% FSA incorporation caused the transformation of Q4 and Q3 to Q2, whereas 50% CGA introduction resulted in the conversion of Q4 and Q2 into Q3 and Q1 + Q0, respectively. The silicate network depolymerised, causing reduction in the ash fusion temperature and increasing the melting rate.