Glycerol, a renewable by-product of biodiesel production, is an increasingly attractive bio-feedstock for conversion into value-added chemicals. Among its transformations, acetalisation to produce solketal and acetal holds promise due to their use as fuel additives, solvents, and polymer precursors. This review critically examines the properties, synthesis, and applications of glycerol, with a focus on heterogeneous catalytic acetalisation using catalysts such as heteropoly acids, metal oxides, and polymer-supported materials. It also analyzes how reaction parameters such as temperature, molar ratio, water content, and time affect conversion and selectivity. Advancements in this area highlight glycerol’s potential in sustainable industrial processes and future biorefineries.