The production of bio-based polymers is crucial for addressing the environmental and socio-economic challenges posed by fossil-based plastics. It is increasingly important to design degradable bio-based polymers, as not all bio-based polymers are biodegradable. Moreover, the exploration of biomass-based diols for creating materials with tunable properties has been limited. α-Pinene, a significant forestry-derived material, has the necessary rigidity to mimic the properties of aromatic, petroleum-based polymers. However, its inert backbone makes it challenging to utilize directly in polymerization. Additionally, during the polymerization of α-pinene-based monomers, ring-opening can be a potential side reaction that negatively affects the material’s properties. In this study, we present a concise and scalable synthesis of two novel α-pinene-derived unsymmetrical bulky chiral diols with extended chains, as well as eight structurally diverse polyesters exhibiting excellent thermal stability. Two of the synthesized polyesters, identified as HN_FDCA and HM_FDCA, demonstrate very high glass transition temperatures of 90 °C and 121 °C, respectively. We also observed various configurations—head-head, tail-tail, and head-tail—where the stereochemistry is influenced by hydrogen bonding. Furthermore, the synthesized polyesters exhibit adhesive properties.  The extended chain structure prevents the ring-opening of α-pinene and allows the bicyclic rings to project from the polymer backbone. The steric hindrance created by the intact bicyclic α-pinene rings protruding from the polymer backbone may facilitate the degradation process, leading to efficient chemical recycling of these polyesters under mild conditions and allowing for the recovery of both monomers. Finally, we evaluated the enzymatic degradation of these polyesters using PETase and Cuitanase, which resulted in a mixture of monomers and short-chain oligomers.