Municipal solid waste incinerator fly ash (MSWI-FA) was used synergistically with volcanic ash (VA) to synthesize Geopolymer cement. The effects of the incorporation of 0%, 30%, and 50% of VA and the alkalinity of activating solution on the structure and properties were studied by using the X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), field emission gun scanning electron microscopy (FEG-SEM), and mechanical testing. The encapsulation efficiency of the cements was carried out by using a toxicity characteristic leaching procedure (TCLP). The geopolymerization of MSWI-FA promoted the formation of new minerals such as Thernadite (Na₂SO₄), Hydrocalumite (Ca₄Al₂O₆(CO₃)_0.67(SO₃)_0.33), C-S-H, and Faujasite-Na(Na₂Ca)_0.075(Al_0.3Si_0.7)O₂(H₂O)_0.22. The Geopolymer cement synthesized with the addition of 50% of VA at 6M NaOH concentration, which exhibited the most compact microstructure. This was the highest strength with the best encapsulation ability. The microstructure analysis of the MSWI-FA-VA system revealed the coexistence of C-S-H and N-A-S-H phases as the main cementitious binders. The TCLP results of cement vis a vis raw MSWI-FA showed the leaching of metals reduced to a great extent. This was much lower than the permissible limit fixed by the United States Environmental Protection Agency (USEPA) for the toxicity characteristic. Furthermore, an attempt was made to correlate the microstructure with mechanical properties.