This study investigates the process of long-term (bio)degradation of polyethylene (PE) in an old municipal waste landfill (MWL) and its implications for environmental and human health. Advanced techniques, such as ICP–ES/MS and IC–LC, were used to analyze heavy metals and anions/cations, demonstrating significant concentration deviations from control samples. The soil’s chemical composition revealed numerous hazardous organic compounds, further indicating the migration of additives from PE to the soil. Toxicological assessments, including Phytotoxkit FTM, Microtox® bioassay, and Ostracodtoxkit®, demonstrated phytotoxicity, acute toxicity, and high mortality in living organisms (over 85% for Heterocypris Incongruens). An unusual concentration of contaminants in the MWL’s middle layers, linked to Poland’s economic changes during the 1980s and 1990s, suggests increased risks of pollutant migration, posing additional environmental and health threats. Moreover, the infiltration capability of microorganisms, including pathogens, into PE structures raises concerns about potential groundwater contamination through the landfill bottom. This research underscores the need for vigilant management and updated strategies to protect the environment and public health, particularly in older landfill sites.