The supply of waste glycerol is rising steadily, partially due to the increased global production of biodiesel. Global biodiesel production totals about 47.1 billion liters and is a process that involves the co-production of waste glycerol, which accounts for over 12% of total esters produced. Waste glycerol is also generated during bioethanol production and is estimated to account for 10% of the total sugar consumed on average. Therefore, there is a real need to seek new technologies for reusing and neutralizing glycerol waste, as well as refining the existing ones. Biotechnological means of valorizing waste glycerol include converting it into gas biofuels via anaerobic fermentation processes. Glycerol-to-bioenergy conversion can be improved through the implementation of new technologies, the use of carefully selected or genetically modified microbial strains, the improvement of their metabolic efficiency, and the synthesis of new enzymes. The present study aimed to describe the mechanisms of microbial and anaerobic glycerol-to-biogas valorization processes (including methane, hydrogen, and biohythane) and assess their efficiency, as well as examine the progress of research and implementation work on the subject and present future avenues of research.