The extent of participation of side-chain functionalities during the 1,5,7-triazabicyclo[5.4.0]dec-5-ene (TBD) organobase-catalyzed ring-opening polymerizations (ROP) of six-membered cyclic d-glucose-based carbonates was found to result in significantly different regiochemical outcomes. High regioselectivity was observed for naturally derived poly(4,6-d-glucose carbonate)s (PGCs) containing carbonate side chain substituents in the 2- and 3-positions, whereas regioirregularity was found for analogous PGCs with ether side-chain substituents. The backbone connectivities and structural details of these PGCs were examined through a combination of comprehensive 1D and 2D NMR studies on unimers and dimers, verifying the ring-opening preferences and indicating the contribution of side-chain functionalities in regioselective ROP processes. A molecular understanding of the curious role of side-chain functionalities was demonstrated via density functional theory calculations, revealing stabilization effects of intermolecular hydrogen bonding between the side-chain functionalities and TBD in the transition states. Overall, this work provides fundamental insights into the organocatalytic ROP of these specific six-membered asymmetric cyclic glucose carbonates. More importantly, these findings serve as a foundation for future design strategies that incorporate adjacent functionalities within monomers to act as directing groups and impart molecular interactions that define regiochemical ring-opening.