The bioremediation of polycyclic aromatic hydrocarbons (PAHs) may be facilitated by the presence of heavy metals (HMs) via extracellular polymeric substances (EPSs). However, the variability of EPS characteristics influenced by HMs in relation to PAHs degradation remains uncertain, particularly in the case of fungi. It is therefore crucial to elucidate the impact of HMs on the characteristics of EPSs and their interaction in the process of PAHs biodegradation. The present study observed the cell membrane of Mucor mucedo under conditions of Cu2+ and Pb2+ stress, as well as determining the characteristics of EPSs. The findings demonstated that the presence of HM ions led to a disruption of the fungal cell membrane. The production of EPSs, the content of their main components and EPS property exhibited changes in accordance with the increasing concentration of HMs. It is noteworthy that the degradation of pyrene was enhanced as the concentration of HMs within the range of 0–80 mg L−1, particularly in the presence of EPSs. A positive correlation was observed between pyrene degradation and the total organic carbon, total nitrogen, polysaccharides, proteins, and surface tension of EPSs. It was thus demonstrated that pyrene biodegradation was enhanced under the stress of HMs (less than 80 mg L−1) by varying the characteristics of EPSs. The conceptual framework outlines the pyrene biodegradation process by EPSs under HM stress. This study provides new insights into the potential mechanism by which HMs influence the biodegradation of PAHs through the involvement of EPSs.