In summary, we have successfully synthesized two novel, rigid, unsymmetrical chiral pinene-derived diols in a single step from commercially available starting materials on a large scale in good yields. Both the synthesized diols were utilized for the synthesis of bio-based polyesters under solvent-free conditions in the presence of a metal catalyst via transesterification followed by polycondensation. Polymerization of the two pinene-based diols with one bio-based aromatic and three aliphatic diesters resulted in eight structurally interesting polyesters in which the bicyclic ring structure of the α-pinene is intact and possesses high thermal stability. When the diester is an aromatic crystalline compound, the resulting polyester is semi-crystalline, but the stereochemistry (syndiotactic/isotactic) is controlled by H-bonding stabilization confined by the bicyclic core. The tail-tail, head-tail, and head-tohead configurations were also observed for HN_FDCA (1:2:3) and HM_FDCA (1:2:1) polymers in addition to stereoisomerism. When the diester is an aliphatic compound, then the polyester will be atactic and amorphous. Both the monomers were recovered from the polymers by chemical recycling catalyzed by CaO in excellent yields and the recycled monomers can be reused in polymerization. In addition, the polyesters were degraded into a mixture of oligomers and monomers by PETase and Cutinase enzymes even without pre-treatment. Our results highlight the potential of multicyclic bio-based diols in achieving polyesters with protruding ring structures to give properties approaching that of fossil-based materials without the need for excessive alkyl chain length elongation.