Upon the raising of environmental awareness, the transition from unsustainable polymers based on fossil resources to sustainable bio-based materials has become a hot topic. Since then, researchers are developing new monomers derived from natural resources to meet the global need in commodity polymers and to replace those based on fossil feedstock. Levoglucosenone (LGO) is a readily accessible chiral molecule from the acid-catalyzed flash pyrolysis of cellulose that can be used as a versatile platform for a wide range of high value-added compounds. This chapter focuses on the new, yet rapidly evolving, field of LGO-derived monomers and their utility in the synthesis of polymers via different polymerization methods. Special considerations are given to the evaluation of the monomer syntheses and polymerization processes under the scope of green chemistry. The discussion is supported by the measurement of both atom economy and E factor, in order to assess the sustainability, as well as to provide a framework that allows the comparison between different approaches.