Natural molecular biomass plays an important role in the field of renewable polymers, as they can be directly used or derivatized as monomers for controlled polymerization, in a way similar to many petroleum-derived monomers. We deliver this perspective primarily based on a monomer approach. Biomass-derived monomers are separated into four major categories according to their natural resource origins: (1) oxygen-rich monomers including carboxylic acids (lactic acid, succinic acid, itaconic acid, and levulinic acid) and furan; (2) hydrocarbon-rich monomers including vegetable oils, fatty acids, terpenes, terpenoids and resin acids; (3) hydrocarbon monomers (bio-olefins); and (4) non-hydrocarbon monomers (carbon dioxide). A variety of emerging synthetic tools (controlled polymerization and click chemistry) are particularly summarized. An overview on future opportunities and challenges, which are critical to promote biorefinery in the production of renewable chemicals and polymers, is given.