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 (Na 2 SO 4 ), Hydrocalumite (Ca 4 Al 2 O 6 (CO 3 ) 0.67 (SO 3 ) 0.33 ), C-S-H, and Faujasite-Na(Na 2 Ca) 0.075 (Al 0.3 Si 0.7 )O 2 (H 2 O) 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.Recycling 2018, 3, 50 2 of 14 of heavy metals content. Therefore, MSWI-FA is classified as a hazardous waste [3,4]. Owing to its chemistry, fine particle size, and pozzolanic behavior, MSWI-FA has the potential to be used as a mineral additive in cement. However, its high chlorine content restricts its application in construction material. Although the cement paste is not much affected by chloride except for increased solubilization of cement solids, chlorine is detrimental to the passivation of embedded steel [5]. To avoid this problem, some pre-treatment methods such as water washing and thermal treatment have been proposed [3,6,7]. These pre-treatments certainly eliminate the chlorides and inorganic salts in MSWI-FA but generate other wastes and increase the quantity of energy required for the synthesis and the total cost of the product. The efficient way to valorize MSWI-FA in construction is its use in the process, which displays limited signs of heavy metals leaching and the formation of the corrosion product in the presence of chlorine such as geopolymerization [8][9][10].Geopolymer cement are considered eco-friendly binder materials and potential alternative to Portland cement (OPC) in specific applications since they produce around 80% less CO 2 than Portland cement [11]. It has the potential to use alumina-silicate materials either from natural occurring waste, synthetic waste, or from industrial waste. Thus, varieties of alumina-silicate and industrial waste used for Geopolymer cement synthesis involve volcanic ash, glass powder,...