Over the years, anaerobic digestion (AD) has evolved as a competent technology to retrieve energy potential from various organic substrates, including wastewater. However, the energy metabolisms of anaerobic microorganisms, biochemical reactions, and biogas production are affected by various parameters, including heavy metals. It is important to understand the interaction of heavy metals with anaerobes and their potential influence on the process to enhance energy potential. This review methodically outlines the occurrence and role of heavy metals in the AD process. Additionally, the repercussions of the most common heavy metals (i.e., Cu, Zn, Cd, Fe, and Ni) on each stage of AD (i.e., hydrolysis, acidogenesis, and methanogenesis) have been discussed. We found that traces of heavy metals can endorse anaerobic digestion, but inhibition increases with increasing concentration. Methanogenic archaea are more susceptible to heavy metal inhibition than hydrolytic and acidogenic archaea. An improved understanding and relevant intuition will help to promote biogas production along with heavy metal management.