Degradable polymers based on α-hydroxy acids and α-amino acids constitutes a potent class of biomaterials, combining high hydrolyzability with structural features that mimics peptides. Driven by the design criteria to construct isolated α-amino acid units along a main polylactide chain, a copolymer system was developed based on two monomers with distinctly different equilibrium behaviors. This was uncovered by detailed understanding on the kinetic and thermodynamic polymerizability of 3S,6S-dimethylmorpholine-2,5-dione (DMMD) and L-lactide (LLA) at low reaction temperatures. Under Brønsted base-promoted ring-opening copolymerization (ROCOP) conditions, the equilibrium nature of the copolymerization was shown susceptible to changes in the system, such as catalyst basicity, solvent polarity and initial monomer concentrations. Subsequently, high equilibrium conversions of both monomers with control over molecular weight and dispersity could be achieved within short reaction times by modulation of these factors. Thermodynamic elucidations of the copolymerization system revealed that DMMD behaved as an unstrained monomer with a large propagation barrier, favored by an increase in polymerization temperature. Ultimately, the high propagation barrier of DMMD in the system resulted in a kinetically controlled mechanism with the formation of completely isolated units of DMMD along the polylactide backbone. These results extend current ROCOP strategies of morpholine-2,5-diones and cyclic esters to a mild and selective copolymerization platform for the construction of sequence-controlled α-amino acid decorated polyesters for medical applications.