This paper discusses the possibility of using the process of geopolymerization to immobilize ash from municipal waste incineration plants. Fly ash used in the related research came from the same incineration plant, one of the biggest in Poland. The examination was conducted on the waste samples labeled as 190107* and 190113*. The comparison included such properties of waste as chemical composition, dioxin content, and size and morphology of particles. The waste was solidified in geopolymer matrix made from (i) fly ash from the combustion of bituminous coal or (ii) metakaolin. The waste percentages were 50 mass% and 70 mass%, respectively. Moreover, leaching tests were carried out and mechanical properties of the geopolymers materials containing immobilized ashes were analyzed. It was proved that geopolymerization process allows for the high-level immobilization of compounds and elements such as chlorides, sulfates, fluorides, barium, and zinc. Additionally, it was observed that in the case of the geopolymer samples containing 70 mass% of 190107* waste, the average compressive strength exceeded 18 MPa. Implications: A novel aspect of the results presented in this paper is the comprehensive investigation of the immobilization of large amounts of hazardous waste by means of the synthesis of geopolymers from metakaolin or coal fly ash. According to these results, it was determined that the level of immobilization is much higher in the case of the geopolymers based on metakaolin in comparison with geopolymers made from coal fly ash. On the basis on the obtained results, investigated geopolymers may be successfully used, e.g., as barriers or linear drains in landfills.