Heavy metal contamination in soils has become one of the most critical environmental issues. The most efficient in-situ remediation technique is chemical immobilization that uses cost-effective soil amendments such as phosphate compounds to decrease Pb, Cd and Zn accessibility in the contaminated soils. The present study examined the effectiveness of KH2PO4 in immobilizing Pb, Cd and Zn in three samples of contaminated soils collected from ZGH “Bolesław” (Mining and Smelting Plant “Bolesław”). Effectiveness was evaluated using the following methods: a toxicity characteristic leaching procedure (TCLP)-based experiment, sequential extraction, X-ray diffraction analyses (XRD), and scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS). The most efficient percentage reduction of total leachable metal concentration assessed by TCLP was observed for lead (50%–80%), and the least reduction was observed for zinc (1%–17%). The most effective immobilization of stable compounds assessed by sequential extraction was noted for lead, while the weakest immobilization was noted for cadmium. New insoluble mineral phases were identified by SEM-EDS analysis. Cd, Zn, and Pb formed new stable mineral substances with phosphates. The predominant crystal forms were dripstones and groups of needles, which were easily formed by dissolved carbon rock surfaces containing zinc ions. The alkaline nature of the soil and a large number of carbonates mainly influenced the formation of new structures.