Portland cement has been suggested as an effective stabilization (physico-chemical) method for hazardous waste. This research explored the immobilization of metals in various mixtures of Portland cement and fly ash waste sampled from coal power plant in the province of Lodz, central Poland. The stabilization of fly ash in Portland cement was investigated under a wide range of pH conditions (3–12). Leachability tests were used to determine the efficiency of the encapsulation by studying the dissolution of alkaline metals (sodium, potassium) and alkaline earth metals (calcium, magnesium). The lowest value of leached metals was obtained for ratio of ash to cement of 1:10 in a case of sodium and calcium, while ratio 1.5 gave the lowest leached effects for potassium and magnesium. The high effectiveness of solidification/stabilization process was gained in high pH values (9–11).