The adverse effects of climate change, predominantly propelled by greenhouse gas emissions from fossil fuels, underscore the urgency of seeking sustainable alternatives to fossil fuel use. Amid growing concerns about climate change caused by fossil fuels and petrochemicals, this review focuses on sustainable solutions through the conversion of glycerol into value-added biochemicals. Glycerol, as the main byproduct of biodiesel production, is a particularly attractive chemical due to its potential to be upgraded into value-added building blocks and biochemicals. This review provides a detailed analysis of different thermochemical (catalytic) and synthetic biology (fermentative) pathways for the conversion of glycerol into 1,2-propanediol and 1,3-propanediol, which have proven industrial and commercial applications globally. The synthesis of propanediol from glycerol hydrogenolysis and other catalytic processes using different active metals and acidic oxides is reviewed. The reaction mechanism involved in hydrogenolysis reactions concerning the surface reaction mechanism is systematically discussed. The metabolic activities of promising microorganisms in fermenting glycerol, as the carbon source used to produce propanediol, are illustrated and elaborated. Combining these insights, this review is a comprehensive resource that can foster a better understanding of glycerol transformation into propanediol and its implications for sustainable chemistry and industrial practices. This exploration of alternative methods emphasizes the potential of sustainable approaches to reshape production practices and contribute to climate change mitigation.