Biodiesel is one of the most attractive sources of clean energy. It is produced by the transformation of vegetable oils with up to 10% formation of glycerol as a by-product. Therefore, development of new approaches for processing bio-glycerol into such value-added chemical compounds as solketals is necessary. Thus, various six-and five-membered cyclic compounds can be prepared by acetalization of glycerol with aldehyde or ketone. The resulting glycerol oxygenates are excellent fuel additives that increase viscosity, octane or cetane number, and stability to oxidation. In addition, these products significantly reduce carbon monoxide emissions from standard diesel fuel. In this review, we highlight recent advances in the glycerol valorization for the sustainable production of bio-additives. The review includes a discussion of the innovative and potential catalysts to produce solketals.