We live in a world of synthetic polymers which are used everywhere and everyday. More than 200 pounds of synthetic polymers are consumed per person each year. However, the majority of these polymers are derived from petroleum, a limited, non-renewable resource. On the other hand, the use of polymers in disposable consumer goods has grown tremendously over the past few decades. To reduce the demand for landfill space to pile up the polymer wastes and the consumption of limited petroleum reserves, the development of biodegradable polymer from biorenewable resource has become a subject of concern. In this presentation, I will talk about our efforts on developing the new proton-transfer polymerization (HTP) methodology to convert commercially available and biomass-derived dimethacrylates uniquely into biodegradable polyesters by organic catalyst. In addition, the creating of truly sustainable polymer, which is biorenewable and completely recyclable, via ring-opening polymerization of the previously claimed “non-polymerizable” five-membered lactones will also be discussed.